CN107922254A

CN107922254A - The manufacture method of glass with fine structure

Info

Publication number: CN107922254A
Application number: CN201680049431.4A
Authority: CN
Inventors: 平沼裕司
Original assignee: Nippon Sheet Glass Co Ltd
Current assignee: Nippon Sheet Glass Co Ltd
Priority date: 2015-08-31
Filing date: 2016-08-29
Publication date: 2018-04-17
Also published as: TW201722881A; KR20180048891A; JPWO2017038075A1; US20180340262A1; WO2017038075A1; TWI712568B

Abstract

The present invention provides the formation in the hole for suppressing low pitch, the manufacture method of the glass with fine structure of fine structure such as hole or groove formed with glacing flatness higher and depth on the thickness direction of substrate.The present invention relates to a kind of manufacture method of the glass with fine structure, it has the etching work procedure for irradiating ultrasonic wave to glass to be etched, etching solution used includes hydrofluoric acid in the etching work procedure, more than a kind of the inorganic acid and surfactant in nitric acid, hydrochloric acid and sulfuric acid, in the etching solution, hydrofluoric acid concentration is the mass % of 0.05 mass %~8.0, and inorganic acid concentration is the mass % of 2.0 mass %~16.0, and the content of surfactant is 5ppm~1000ppm.

Description

The manufacture method of glass with fine structure

Technical field

The present invention relates to as caused by laser pulse through hole, have the fine structures such as bottom outlet, groove glass system Make method.More specifically, it is related to a kind of manufacture method of glass, it is rotten to be formed by irradiating laser to glass substrate etc. Portion or processing hole, and by going bad portion to this or processing hole carries out ultrasonic irradiation etching and carries out removing processing, so as to obtain Glass formed with the fine structure.

Background technology

It is etched as the glass substrate to foring rotten portion or small processing hole so as to shape on the glass substrate Into required hole or the method for groove, For example, Patent Document 1 discloses rotten so as to be formed to glass irradiation laser pulse Portion, and use etch-rate (hereinafter also referred to as etching speed) bigger that the glass substrate is compared to the etch-rate in the portion that goes bad Etching solution be etched so as to the method that forms hole or groove.In addition, Patent Document 2 discloses become a part for substrate Matter, and to the partial illumination laser so as to after forming small processing hole, is processed substrate by being etched Method.That is, as shown in Figure 1, being etched to the glass substrate 11 for foring rotten portion or small processing hole so as to form institute The hole needed.

Glass substrate formed with through hole etc. is particularly used for electric substrate purposes situations such as interpolater etc., after consideration Continuous electrode forming process etc., in order to further ensure stable electric current, it is expected that the glacing flatness of such as through hole is high.

However, patent document 1,2 etc. is in the prior art, and it is smaller by the gradient for etching the hole formed, can not sometimes yet Form deep hole.Due to widen by etching fine rotten portion or processing hole so as to form required shape, The etch-rate of base glass material is not zero.Further, since discrepancy of the etching solution inside fine rotten portion or processing hole is difficult, Even if therefore making the stirrer of bar-shaped, tabular or spiral pulpous state be rotated in etching liquid cell or stirring etching solution using bubbling, Etching is also that the part near substrate surface is very fast, and slower inside substrate.Etch-rate in rotten portion is than rotten portion For item as discrepancy or displacement of the situation of part bigger in addition for the etching solution, gradient is being formed greatly simultaneously And very big key element is not occupied in terms of the purpose in the high hole of glacing flatness.However, to possess beyond rotten portion and rotten portion In the case that the glass of the less characteristic of difference of partial etch-rate is object, it is until rotten portion is etched to inside substrate Only, around the rotten portion near substrate surface, the etching of the part beyond rotten portion is all carrying out, the difference of the etch-rate It is smaller, the problem of hole gradient in the rotten portion near substrate surface as shown in Figure 2 diminishes may more occur.

Prior art literature

Patent document

Patent document 1：Japanese Unexamined Patent Publication 2011-37707 publications

Patent document 2：Japanese Unexamined Patent Publication 2001-105398 publications

The content of the invention

Technical problems to be solved by the inivention

The invention that the present invention is in view of the above problems and completes, its object is to, there is provided one kind has and uses laser arteries and veins The manufacture method of the glass of the fine structure of punching, this method suppress the formation for possessing the hole of the low pitch of the fine structure, obtain To the glass of the fine structure such as the hole formed with glacing flatness higher and depth on the thickness direction of glass substrate or groove.Particularly There is provided a kind of has and the manufacture method of glass with the fine structure of laser pulse, this method suppress possess the fine structure The formation in the hole of low pitch, obtains on the thickness direction of glass substrate the passing through formed with glacing flatness higher as fine structure The glass of through hole.In addition, it is an object of the present invention to provide industrial favourable and used laser pulse and have fine knot The manufacture method of the glass of structure.

Means for solving the problems

The present invention provides a kind of manufacture method of the glass with fine structure, it has irradiates ultrasonic wave to carry out to glass The etching work procedure of etching, etching solution used includes hydrofluoric acid in the etching work procedure, and 1 in nitric acid, hydrochloric acid and sulfuric acid The inorganic acid and surfactant of kind of the above, in the etching solution, hydrofluoric acid concentration is the mass % of 0.05 mass %~8.0, Inorganic acid concentration is the mass % of 2.0 mass %~16.0, and the content of surfactant is 5ppm~1000ppm.

Invention effect

By using the manufacture method of the glass with fine structure of the present invention, the shape in the hole of low pitch can be suppressed Into manufacturing the hole formed with glacing flatness higher and depth on the thickness direction of substrate or the glass of the fine structure such as groove.Especially Being to provide a kind of has and the manufacture method of glass with the fine structure of laser pulse, this method suppress possess the fine structure Low pitch hole formation, obtain on the thickness direction of glass substrate as fine structure formed with glacing flatness higher The glass of through hole.In addition, it is an object of the present invention to provide industrial favourable and used laser pulse and with fine The manufacture method of the glass of structure.

Brief description of the drawings

Fig. 1 is the schematic cross-section of the engraving method for the glass substrate for representing the prior art.

Fig. 2 is the glass of the less situation of difference for the etch-rate for representing the prior art, particularly rotten portion and glass substrate The schematic cross-section of the engraving method of glass substrate.

Fig. 3 is the schematic cross-section for the formation process for representing the rotten portion involved by embodiment 1.

Fig. 4 is to illustrate the assay method of hole after etching, the schematic cross-section of glass substrate involved by embodiment 1.

Fig. 5 is the image of the observation result in the section after the glass substrate etching involved by embodiment 1.

Fig. 6 is the image of the observation result in the section after the glass substrate etching involved by comparative example 1.

Fig. 7 is the image of the observation result in the section after the glass substrate etching involved by embodiment 12.

Fig. 8 is that the glass substrate involved by embodiment 14 is that rotten portion or processing hole form the observation result before rear, etching Image.

Fig. 9 is the image of the observation result in the section after the glass substrate etching involved by embodiment 14.

Embodiment

The manufacture method of the glass with fine structure of the present invention is characterized in that, have to glass irradiation ultrasonic wave come into The etching work procedure of row etching, etching solution used includes hydrofluoric acid in the etching work procedure, in nitric acid, hydrochloric acid and sulfuric acid More than a kind of inorganic acid and surfactant, in the etching solution, hydrofluoric acid concentration is the mass % of 0.05 mass %~8.0, Inorganic acid concentration is the mass % of 2.0 mass %~16.0, and the content (mass concentration) of surfactant is 5ppm~1000ppm.

The manufacture method of the glass with fine structure of the present invention is preferably also equipped with irradiating to glass before etching work procedure Laser pulse is so as to the process for forming rotten portion or processing hole.That is, in etching work procedure glass used preferably etching work procedure it It is preceding to form rotten portion or processing hole.

Before the detailed content of contact etching and processing, to forming rotten portion on glass or processing the process in hole (below, Also referred to as " rotten portion's formation process ".) be described.

Etch what is removed as predetermined continue through afterwards is formed to form the fine structures such as through hole in glass The process (method) in rotten portion, can use the method described in Japanese Unexamined Patent Publication 2008-156200 publications.That is, by by wavelength X Laser pulse lens assemble and expose to glass, the part that laser pulse is irradiated among glass formed rotten portion or add The method in work hole.

As the glass (hereinafter also referred to as Laser Processing glass) that can be used in the present invention, quartz glass, borosilicate Sour glass, alumina silicate glass, the silicate glass of soda lime glass or titaniferous are suitable with glass as Laser Processing. In addition, in these glass, it is substantially free of the alkali-free glass of alkali composition (alkali metal oxide) or only includes micro alkali composition Glass with lower alkali content etc. is also suitable with glass as Laser Processing.

In addition, in order to effectively improve its absorption coefficient, glass can include selected from Bi, W, Mo, Ce, Co, Fe, Mn, Cr, At least one kind of of the oxide of metal in V and Cu is used as coloring components.

As pyrex, the #7059 glass that can enumerate Corning companies (is formed using quality representation as SiO₂ 49%th, Al₂O₃10%th, B₂O₃15%th, RO (alkaline earth oxide) 25%) or Pyrex (registration mark) (glass numberings 7740) etc..

As the embodiment 1 of alumina silicate glass, there can be following composition.

With quality representation, comprising

SiO₂50~70%,

Al₂O₃14~28%,

Na₂O 1~5%,

1~13% and of MgO

The glass composition of ZnO 0~14%.

As the other embodiment 2 of alumina silicate glass, there can be following composition.

With quality representation, comprising

SiO₂56~70%,

Al₂O₃7~17%,

B₂O₃0~9%,

Li₂O 4~8%,

MgO 1~11%,

ZnO 4~12%,

TiO₂0~2%,

Li₂O+MgO+ZnO 14~23%,

The glass composition of CaO+BaO 0~3%.

As the other embodiment 3 of alumina silicate glass, there can be following composition.

With quality representation, comprising

SiO₂58~66%,

Al₂O₃13~19%,

Li₂O 3~4.5%,

Na₂O 6~13%,

K₂O 0~5%,

R₂10~18% (wherein, R of O₂O=Li₂O+Na₂O+K₂O)、

MgO 0~3.5%,

CaO 1~7%,

SrO 0~2%,

BaO 0~2%,

RO 2~10% (wherein, RO=MgO+CaO+SrO+BaO),

TiO₂0~2%,

CeO₂0~2%,

Fe₂O₃0~2%,

0~1% (wherein, TiO of MnO₂+CeO₂+Fe₂O₃+ MnO=0.01~3%),

SO₃0.05~0.5% glass composition.

As the other embodiment 4 of alumina silicate glass, there can be following composition.

With quality representation, comprising

SiO₂60~70%,

Al₂O₃5~20%,

Li₂O+Na₂O+K₂O 5~25%,

Li₂O 0~1%,

Na₂O 3~18%,

K₂O 0~9%,

MgO+CaO+SrO+BaO 5~20%,

MgO 0~10%,

CaO 1~15%,

SrO 0~4.5%,

BaO 0~1%,

TiO₂0~1%,

ZrO₂0~1% glass composition.

As the other embodiment 5 of alumina silicate glass, there can be following composition.

Included with quality representation

SiO₂59~68%,

Al₂O₃9.5~15%,

Li₂O 0~1%,

Na₂O 3~18%,

K₂O 0~3.5%,

MgO 0~15%,

CaO 1~15%,

SrO 0~4.5%,

BaO 0~1%,

TiO₂0~2%,

ZrO₂1~10% glass composition.

Soda lime glass is to be widely used in the glass composition of such as glass sheet.

As the embodiment 1 of the silicate glass of titaniferous, there can be following composition.

Represented with a mole %, comprising

TiO₂5~25%, and

SiO₂+B₂O₃For 50~79%,

Al₂O₃+TiO₂For 5~25%,

Li₂O+Na₂O+K₂O+Rb₂O+Cs₂O+MgO+CaO+SrO+BaO is 5~20%

Glass composition.

In addition, in the embodiment 1 of the silicate glass of above-mentioned titaniferous, preferably represented with a mole %, comprising

SiO₂60~65%, TiO₂12.5~15%, Na₂O 12.5~15%, and SiO₂+B₂O₃For 70~75%.

In addition, in the embodiment 1 of the silicate glass of above-mentioned titaniferous, more preferably meet following formula (Al₂O₃+TiO₂)/ (Li₂O+Na₂O+K₂O+Rb₂O+Cs₂O+MgO+CaO+SrO+BaO)≤0.9 (in formula, the amount of each component represents for mole %.).

In addition, the other embodiment 2 of the silicate glass as titaniferous, can have following composition.With a mole % Represent, comprising

B₂O₃10~50%,

TiO₂25~40%, and

SiO₂+B₂O₃For 20~50%,

Li₂O+Na₂O+K₂O+Rb₂O+Cs₂O+MgO+CaO+SrO+BaO is 10~40%

Glass composition.

As the embodiment 1 of glass with lower alkali content, there can be following composition.

Represented with a mole %, comprising

SiO₂45~68%,

B₂O₃2~20%,

Al₂O₃3~20%,

TiO₂0.1~5.0% (but except 5.0%),

ZnO 0~9%, and

Li₂O+Na₂O+K₂O is the glass composition of 0~2.0% (but except 2.0%).

In addition, in the embodiment 1 of the glass with lower alkali content, as coloring components, preferably represent to include with a mole % CeO₂0~3.0%, Fe₂O₃0~1.0%.In addition, in the embodiment 1 of above-mentioned glass with lower alkali content, more preferably it is substantially free of Alkali metal oxide (Li₂O+Na₂O+K₂O alkali-free glass).

The glass with lower alkali content or alkali-free glass of the above embodiment 1 include TiO₂As essential component.The glass with lower alkali content or TiO in alkali-free glass₂Content for 0.1 mole of % less than 5.0 moles of %, from the hole inner wall irradiated by laser This excellent point of flatness in face sets out, preferably the % of 0.2~4.0 mole of %, more preferably 0.5~3.5 mole, further preferred 1.0 ~3.5 moles of %.TiO is moderately included by making to have in the glass with lower alkali content or alkali-free glass that specifically form₂Even if pass through phase Rotten portion can be also formed to energy exposures such as weak laser, and the rotten portion brings and etched by the ultrasonic irradiation of rear process Such effect can easily be removed.Additionally, it is known that TiO₂Combination can be unanimous on the whole with the energy of ultraviolet light, purple can be absorbed Outer light.TiO is included by appropriateness₂, can also as is generally known in a manner of electric charge movement absorbs using with other The interaction of toner colours to control.Therefore, TiO is passed through₂Content adjustment, absorption of the glass to defined light can be made For appropriateness.By making glass have appropriate absorption coefficient, the formation in the rotten portion for forming hole using etching becomes easy, therefore From these viewpoints it is also preferred that appropriateness includes TiO₂。

In addition, the glass with lower alkali content or alkali-free glass of the embodiment 1 can include ZnO as optional member.It is described low The content of ZnO is preferably 0~9.0 mole of %, is more preferably 1.0~8.0 moles of %, is further excellent in alkali glass or alkali-free glass Elect 1.5~5.0 moles of %, particularly preferably 1.5~3.5 moles of % as.ZnO is and TiO₂Equally shown in UV light region Go out the component of absorption, therefore be if the component for carrying out useful effect to glass tape of the invention comprising if.

The glass with lower alkali content or alkali-free glass of the embodiment 1 can contain CeO₂As coloring components.Especially by And use TiO₂, rotten portion can be more easily formed.CeO in the glass with lower alkali content or alkali-free glass₂Content be preferably 0~3.0 Mole %, more preferably 0.05~2.5 mole of %, more preferably 0.1~2.0 mole of %, particularly preferably 0.2~0.9 Mole %.

Fe₂O₃Coloring components as the glass used in the present invention are also effective, can also contain Fe₂O₃.Particularly By and use TiO₂And Fe₂O₃, or and use TiO₂、CeO₂And Fe₂O₃, the formation in rotten portion becomes easy.The glass with lower alkali content Or Fe in alkali-free glass₂O₃Content be preferably 0~1.0 mole of %, more preferably 0.008~0.7 mole of %, further preferably For 0.01~0.4 mole of %, particularly preferably 0.02~0.3 mole of %.

The glass with lower alkali content or alkali-free glass of the embodiment 1 are not limited to the component that the above is enumerated, but by containing appropriateness Coloring components, can make glass provision wavelengths (below wavelength 535nm) absorption coefficient for 1~50/cm, be preferably 3~ 40/cm。

In addition, the other embodiment 2 as glass with lower alkali content, can have following composition.

Represented with a mole %,

SiO₂45~70%,

B₂O₃2~20%,

Al₂O₃3~20%,

CuO 0.1~2.0%,

TiO₂0~15.0%,

ZnO 0~9.0%,

Li₂O+Na₂O+K₂The glass composition of O 0~2.0% (but except 2.0%).

In addition, in the embodiment 2 of the glass with lower alkali content, alkali metal oxide (Li is more preferably substantially free of₂O+Na₂O+ K₂O alkali-free glass).

The glass with lower alkali content or alkali-free glass of the embodiment 2 can be with the glass with lower alkali content or alkali-free of the embodiment 1 Glass similarly includes TiO₂.TiO in the glass with lower alkali content or alkali-free glass of the embodiment 2₂Content rub for 0~15.0 Your %, it is preferably 0~10.0 mole of %, more excellent from this excellent point of the flatness of the hole internal face irradiated by laser Select 1~10.0 mole of %, further preferred 1.0~9.0 moles of %, particularly preferred 1.0~5.0 moles of %.

In addition, the glass with lower alkali content or alkali-free glass of the embodiment 2 can include ZnO.The low alkali of the embodiment 2 The content of ZnO is 0~9.0 mole of %, is preferably 1.0~9.0 moles of %, is more preferably 1.0~7.0 in glass or alkali-free glass Mole %.ZnO is and TiO₂The component of absorption is equally shown in UV light region, thus be if comprising if to the present invention Glass tape carry out the component of useful effect.

In addition, the glass with lower alkali content or alkali-free glass of the embodiment 2 include CuO.The glass with lower alkali content or alkali-free glass The content of middle CuO is preferably 0.1~2.0 mole of %, more preferably 0.15~1.9 mole of %, more preferably 0.18~1.8 Mole %, particularly preferably 0.2~1.6 mole of %.By comprising CuO, being coloured in glass, at the wavelength for making regulation laser Absorption coefficient in appropriate scope, so as to suitably absorb the energy of irradiation laser, and can be readily formed into For the rotten portion of hole basis of formation.

The glass with lower alkali content or alkali-free glass of the embodiment 2 are not limited to the component that the above is enumerated, but by containing appropriateness Coloring components, can make glass provision wavelengths (below wavelength 535nm) absorption coefficient for 1~50/cm, be preferably 3~ 40/cm。

The glass with lower alkali content or alkali-free glass of the embodiment 1 and 2 can include MgO as optional member.MgO is in alkaline earth There is the increase for suppressing thermal coefficient of expansion among quasi-metal oxides and strain point will not be made too to reduce such feature, Also dissolubility is improved, therefore MgO can be contained.The content of MgO is preferably 15.0 to rub in the glass with lower alkali content or alkali-free glass That below %, more preferably 12.0 moles of below %, more preferably 10.0 moles of below %, particularly preferably 9.5 rub You are below %.In addition, the content of MgO is preferably 2.0 moles of more than %, more preferably 3.0 moles of more than %, is more preferably 4.0 moles of more than %, particularly preferably 4.5 moles of more than %.

The glass with lower alkali content or alkali-free glass of the embodiment 1 and 2 can include CaO as optional member.CaO and MgO It is identical, there is the increase for suppressing thermal coefficient of expansion and strain point will not be made too to reduce such feature, also put forward dissolubility Height, therefore CaO can be contained.In the glass with lower alkali content or alkali-free glass the content of CaO be preferably 15.0 moles of below %, it is more excellent Elect 12.0 moles of below %, more preferably 10.0 moles of below %, particularly preferably 9.3 moles of below % as.In addition, The content of CaO be preferably 1.0 moles of more than %, more preferably 2.0 moles of more than %, more preferably 3.0 moles of more than %, Particularly preferably 3.5 moles of more than %.

The glass with lower alkali content or alkali-free glass of the embodiment 1 and 2 can include SrO as optional member.SrO and MgO It is identical with CaO, there is the increase for suppressing thermal coefficient of expansion and strain point will not be made too to reduce such feature, also make molten Solution property improves, therefore in order to which devitrification characteristic and acid proof improvement can contain SrO.In the glass with lower alkali content or alkali-free glass The content of SrO be preferably 15.0 moles of below %, more preferably 12.0 moles of below %, more preferably 10.0 moles of % with Under, particularly preferably 9.3 moles of below %.In addition, the content of SrO is preferably 1.0 moles of more than %, more preferably 2.0 rubs You are more than %, more preferably 3.0 moles of more than %, particularly preferably 3.5 moles of more than %.

" being substantially free of " certain component refers to that the content of the component in glass is less than 0.1 mole of %, preferably smaller than 0.05 rubs You are %, more preferably 0.01 mole of below %.It should be noted that in this specification, number range (content of each component, by The calculated value of each component and each physical property etc.) upper limit value and lower limit can be appropriately combined.

The thermal coefficient of expansion of the glass used in the present invention is preferably 100 × 10^-7/ DEG C below, more preferably 70 × 10^-7/ Below DEG C, more preferably 60 × 10^-7/ DEG C below, particularly preferably 50 × 10^-7/ DEG C below.In addition, thermal coefficient of expansion Lower limit is not particularly limited, such as can be 10 × 10^-7/ DEG C more than or 20 × 10^-7/ DEG C more than.

Thermal coefficient of expansion is carried out as follows measure.First, diameter 5mm, the cylindrical glass specimen of height 18mm are made.Will Untill it is heated to the yield point of glass specimen from 25 DEG C, by measuring the elongation percentage of glass specimen at each temperature, heat is calculated The coefficient of expansion.The average value of the thermal coefficient of expansion of 50~350 DEG C of scopes is calculated, mean thermal expansion coefficients can be obtained.Evenly heat The coefficient of expansion can pass through thermo-mechanical analysis device (TMA:Thermomechanical analyzer) it is measured.Actual The measure of thermal coefficient of expansion uses the thermo-mechanical analysis device TMA4000SA of NETZSCH companies, in 5 DEG C/min of programming rate Under the conditions of be measured.

The shape of glass is not limited, such as glass plate can be used.It should be noted that in rotten portion's formation process, The use of so-called photosensitive glass is not necessary, the scope of machinable glass is very wide.That is, rotten portion of the invention forms work In sequence, the glass for being substantially free of gold, silver can be processed.

The particularly high glass of rigidity, when laser irradiates, any one of the upper and lower surface of glass is difficult to produce Raw crackle, can be suitably processed by rotten portion's formation process of the present invention.For example, it is preferable to Young's modulus is 80GPa Glass above.

It should be noted that absorption coefficient can pass through the transmitance and reflectivity of the glass substrate for measuring thickness t (cm) To calculate.For the glass substrate of thickness t (cm), using spectrophotometer (for example, the ultraviolet of Japan Spectroscopy Corporation can See near infrared spectrometer V-670) the transmitance T (%) and incidence angle at wavelength (below wavelength 535nm) place as defined in measure Reflectivity R (%) under 12 °.By the measured value of gained absorption coefficient is calculated using following formula.

α=(1/t) * ln { (100-R)/T }

The absorption coefficient of the glass used in the present invention is preferably 1~50/cm, more preferably 3~40/cm.

Market is on sale sometimes for the glass enumerated above, can be commercially available.In addition even in market without situation about selling Under, required glass can be made with known manufacturing process (for example, press over system, float glass process, slot draw method, the tape casting etc.) Glass, further can obtain the glass composition of target shape by the post-processing such as cutting off, grinding.

In rotten portion's formation process, it can be irradiated to form rotten portion with 1 subpulse.That is, can be by irradiate in this process The misaligned mode in position irradiates laser pulse to form rotten portion.However, it is also possible to irradiated in a manner of radiation pulses overlap Laser pulse.

In rotten portion's formation process, usually laser pulse is assembled to focus to the inside of glass with lens.For example, in glass In the case of forming through hole in glass plate, usually laser pulse is assembled to focus near the center in sheet thickness direction. It should be noted that only in the case of the upper surface side (light incident side of laser pulse) of processing glass plate, usually by laser pulse Assemble to focus to the upper surface side of glass plate.On the contrary, only process lower face side (the light incident side phase with laser pulse of glass plate Anti- side) in the case of, usually laser pulse is assembled to focus to the lower face side of glass plate.As long as however, it can be formed Glass goes bad portion, can also be by the outside of focusing laser pulses to glass.For example, it is also possible to by focusing laser pulses to glass it Outside only apart from the upper surface of glass plate or the position of lower surface predetermined distance (such as 1.0mm).In other words, as long as can be on glass Form rotten portion, can also by focusing laser pulses to from the upper surface of glass to (the advance with laser pulse of nearby direction Side is in the opposite direction) certain position (upper surface for including glass) within 1.0mm or from the lower surface of glass rearward Certain position (lower surface position for including glass) or interior within (having passed through the direction that the laser pulse of glass advances) 1.0mm Portion.

In the case of nanosecond laser or its device, the pulse width of laser pulse is preferably 1~200ns (nanosecond), more Preferably 1~100ns, more preferably 5~50ns.In addition, if pulse width is more than 200ns, the spike of laser pulse Value reduces, and can not be processed well sometimes.The laser being made of the energy of 5~100 μ J/ pulses is exposed into above-mentioned laser Processing glass.By increasing the energy of laser pulse, increase the length in rotten portion with being proportional to.Laser pulse Beam quality M₂Value can be such as less than 2.By using M₂It is worth the laser pulse for less than 2, small pore or small recessed The formation of groove becomes easy.It should be noted that it is following, in the present specification, unless stated otherwise, with the relevant explanation of laser It is related to nanosecond laser or its device.

In rotten portion's formation process, laser pulse can be Nd：The higher hamonic wave of YAG laser, Nd：YVO₄The high order of laser Harmonic wave or Nd：The higher hamonic wave of YLF Lasers.Higher hamonic wave is such as the second higher hamonic wave, the 3rd higher hamonic wave or the 4th high order Harmonic wave.The wavelength of second higher hamonic wave of these laser is near 532~535nm.The wavelength of 3rd higher hamonic wave for 355~ Near 357nm.The wavelength of 4th higher hamonic wave is near 266~268nm.By using these laser, can inexpensively add Work glass.

As the device for the Laser Processing being applicable in for the portion's formation process that goes bad, can enumerate for example, Coherent companies The high of system repeats solid pulse UV laser：AVIA355-4500.In the device, as the 3rd higher hamonic wave Nd：YVO₄Laser, weight Complex frequency can obtain the maximum laser power of 6W or so when being 25kHz.The wavelength of 3rd higher hamonic wave is 350~360nm.

The wavelength of laser pulse is preferably below 535nm, for example, can be the scope of 350~360nm.On the other hand, if The wavelength of laser pulse is more than 535nm, then point of irradiation becomes larger, and the making of small construction becomes difficult, and by the influence of heat Cause easily to crack around point of irradiation.

As typical optical system, the laser of vibration is extended to 2~4 times (on the time point with optical beam expander 7.0~14.0mm of processing department spot diameter φ), with after the core of variable aperture cutting laser with galvanometer mirror tune Whole optical axis, adjusts focal position with the f θ lens of 100mm or so and converges to glass.

The focal length L (mm) of lens in the scope of such as 50~500mm, can also be selected from the scope of 100~200mm.

In addition, the beam diameter D (mm) of laser pulse can also be selected from 3~20mm in the scope of such as 1~40mm Scope.Here, beam diameter D is the beam diameter of laser pulse when being incident to lens, is referred to relative to the strong of beam center Intensity reaches [1/e for degree²] times scope diameter.

In rotten portion's formation process, the value i.e. value of [L/D] of focal length L divided by beam diameter D are more than 7, are preferably more than 7 Less than 40 or more than 10 and less than 20.The value is the value related with exposing to the convergence of the laser of glass, which gets over It is small, represent that laser converges at part, is more difficult to make uniform and long rotten portion.If the value is less than 7, near beam waist Laser power is too strong, produces and easily cracks the problem of such in inside glass.

In rotten portion formation process, it is not necessary to which processing (promotes for example, being formed before laser pulse pre-irradiation carries out glass The film of the absorption of laser pulse).However, as long as the effect of the present invention can be obtained, such processing can also be carried out.

Change the size of aperture and laser diameter is changed so as to so that opening number (NA) change to 0.020~ 0.075.If NA becomes too much, the energy of laser only concentrates near focal point, it is impossible on the thickness direction of glass effectively Form rotten portion.

And then by irradiating the less pulse lasers of NA, just formed using pulsatile once irradiation relatively long on thickness direction Rotten portion, therefore the raising to productive temp is effective.

It is preferred that repetition rate is set to 10~25kHz to sample irradiation laser.Additionally by the thickness direction of glass Change focal position, the position (upper surface side or lower face side) in the rotten portion formed on glass can be adjusted to most suitable.

Further by the control from control PC, laser output, action of galvanometer mirror etc. can be controlled, is based on Drawing data is tieed up with the 2 of the making such as CAD software, laser can be exposed on glass substrate with defined speed.

The part being irradiated with a laser forms the rotten portion different from the other parts of glass.The rotten portion can be shown by optics Micro mirror etc. easily distinguishes.Each glass has differences because of composition, but rotten portion is formed as a generally cylindrical.Rotten portion Reach near the upper surface of glass near lower surface.

It is believed that rotten portion is to be irradiated by laser photochemically reactive to occur, the defects of E ' centers and non-bridging oxygen, produces Raw position, either by laser illumination bands Lai instant heating or rapid cooling produce, maintain it is sparse in high-temperature area Glass structure position.

The present invention rotten portion's formation process involved by and with laser irradiation and wet etching venting techniques in, can Rotten portion is formed with the irradiation of a laser pulse.

As the condition selected in rotten portion's formation process, can enumerate for example, the absorption coefficient of glass is 1~50/cm, swashs Light impulse length is 1~100ns, the energy of laser pulse is 5~100 μ J/ pulses, wavelength is 350~360nm, laser pulse Beam diameter D be 3~20mm and combination that the focal length L of lens is 100~200mm.

In addition, as needed, before etching is performed in order to reduce the deviation of the diameter in rotten portion, can to glass plate into Row grinding.Die down if overgrinding to the etch effect in the portion that goes bad, therefore the depth ground is preferably the upper table from glass plate Play 1~20 μm of depth in face.

The size in the rotten portion formed in rotten portion's formation process is according to the beam diameter D of laser when being incident to lens, saturating The focal length L of mirror, the absorption coefficient of glass, laser pulse power etc. and change.A diameter of such as the 5 of the rotten portion of gained ~200 μm or so or 10~150 μm or so.In addition, the depth in rotten portion is because of above-mentioned laser irradiation condition, glass Absorption coefficient, the thickness of slab of glass and it is different, can be such as 50~300 μm or so.

In addition, by the way that multiple holes are continuously formed, groove can be formed.In this case, by be arranged as wire Mode irradiate multiple laser pulses, form the multiple rotten portions for being configured to wire.Thereafter, it is recessed to be formed by etching rotten portion Groove.The irradiation position of multiple laser pulses can be misaligned, and for by etching the hole formed, adjacent hole can tie each other Close.

In addition, the mode of the above is not limited to as the method for forming rotten portion.For example, it is also possible to by from foregoing The irradiation of femtosecond laser and formed rotten portion or processing hole.The situation of femtosecond laser or its device, as long as realizing the present invention Effect, do not limit special condition.For example, the pulse width of laser pulse is preferably 100~2000fs (femtosecond), More preferably 200~1000fs.It is preferred that repetition rate is set to 0.5~10kHz to sample irradiation laser.The energy of laser pulse Preferably 1~20 μ J/ pulses.Additionally, it is preferred that adjustment optical system, so that the laser pulse of 1~20 μ J of every 1 pulse is in target glass The hot spot of 1~30 μm of processing department spot diameter φ is formed on glass.In femtosecond laser or its device, can use will be above-mentioned suitable Condition it is appropriately combined obtained by condition.

Furthermore it is possible to be pre-formed processing hole in glass substrate to replace rotten portion, and pass through the etching of rear process Process ultimately forms the structures such as through hole.The process for forming the processing hole is such process：To for example appropriate glass substrate (for example, reducing to higher silicate glass containing Ti of effect of the processing threshold value of Laser Processing etc.) irradiation possesses defined spy Property laser so that by melt or evaporate formed processing hole.As the laser aid used, preferably such as centre wavelength For 266nm or the YAG laser of 355nm (5~8nm of pulse width), wherein, the focal length L (mm) of lens is such as 50~500mm's Scope, repetition rate are set to 10~25kHz, irradiate laser 0.5~10 second to glass.

By laser ablation, hole or the groove of 10~100 μm or the diameter more than it itself can be being formed, thus it is logical Cross and be used in combination with the etching and processing of rear process, expansion except aperture, in addition to the raising of glacing flatness, also having makes the broken of processing department periphery The deformation position of the glass such as piece becomes unobvious, or removes the effect of fine crackle.

As long as by being used in combination for the etching work procedure with rear process, fine structure can be formed on the glass substrate, and go bad portion Forming method be just not limited to above method.

The manufacturing method of the present invention has the etching work procedure to glass irradiation ultrasonic wave.Cavitate, vibrate caused by ultrasonic wave The product that acceleration and current promotion etching solution and etching tape come disperses untill fine hole or inside grooves.By The irradiation of ultrasonic wave is carried out during etching, eliminates the difference in the substrate surface of fine hole or groove and the internal etching carried out It is different, fine, gradient big (high straightness) and deep hole or groove can be formed.

When the ultrasonic wave is conducted in a liquid, produce and the phenomenon in cavity is formed in liquid cavitate.Cavitation erosion is when extremely short It is interior to boost and be depressured repeatedly, stretched or compressed while hydrone is vibrated, so as to promote etching solution or etching tape The product come is moved untill fine hole or the inside of groove.If however, improve frequency of oscillation, the threshold for generation of cavitating Value improves, particularly if being then increased sharply to exponential function formula more than 100kHz and making cavitation erosion become difficult to occur.From elimination In the substrate surface of fine hole or groove and the internal etch differential carried out, it is big and deep that fine, gradient can be formed The point of hole or groove sets out, ultrasonic irradiation etching frequency of oscillation be preferably below 120kHz scope, more preferably 10~ 120kHz, occurs the point sufficiently to cavitate from etching solution, more preferably 20~100kHz.The frequency of oscillation The frequency of oscillation that two or more kinds may be used.

As the intensity of ultrasonic wave, it is not particularly limited, is preferably 0.10~5.0W/cm², more preferably 0.15~ 4.0W/cm², more preferably 0.20~3.0W/cm².As long as the ultrasonic intensity in the scope, in processed glass In the range of not damaging, the intensity of the ultrasonic wave of irradiation can be improved.Selection above range in ultrasonic wave intensity be because Promote the effect increase of the exchange of the etching solution near inside and outside fine structure, so it is preferred that.The intensity of ultrasonic wave represents output work The floor space of rate (unit W) divided by etching groove (unit cm²) obtained value.

For ultrasonication, it is not particularly limited, known device can be used.It is, for example, possible to use W-113 (model, exports 100W, frequency of oscillation 28kHz/45kHz/100kHz, Honda Electronic's system, groove size：W240× D140 × H100 (unit mm)) or US-3R (model, output power 120W, frequency of oscillation 40kHz, AS ONE Co., Ltd. System, groove size：W303 × D152 × H150 (unit mm)) etc..

In etching work procedure, in order to carry out the etching only from unilateral, can glass plate upper surface side or under Face side coating surface protection fruit glaze agent is protected.As such surface protection fruit glaze agent, commercially available product can be used, can be lifted Go out for example, Silitect-II (Trylaner International company systems) etc..

Etching solution in the ultrasonic irradiation etching of the present invention includes hydrofluoric acid, a kind in nitric acid, hydrochloric acid and sulfuric acid Inorganic acid above, and surfactant.As long as without prejudice to the effect of the present invention, etching solution can also include other compositions.Make For such other compositions, the inorganic acid beyond hydrofluoric acid, nitric acid, hydrochloric acid and sulfuric acid, ethanedioic acid, tartaric acid, iodine second can be enumerated The organic acids such as acid, fumaric acid, maleic acid, chelating agent etc..Chelating agent is by complexing of metal ionization so as to prevent from being re-attached to base Plate surface, therefore be effective.As chelating agent, dimethyl glyoxime, dithizone, oxyquinoline, ethylenediamine tetrem can be enumerated Acid, nitrilotriacetic acid, hydroxy ethylene diphosphonic acid (HEDP), nitrilo trimethylene phosphonic acids (NTMP) etc..HEDP and NTMP It is high in the dissolubility of the acidic region of hydrofluoric acid system, it is effective.In addition, etching solution can also be substantially free of these other into Point.Etching solution " is substantially free of " certain component and refers to, the content of the component is less than 1.0 mass %, preferably smaller than 0.5 in etching solution Quality %, more preferably less than 0.1 mass %.

As the surfactant that can be used in the present invention, amphoteric surfactant can be enumerated, cationic surface is lived Property agent, anion surfactant, nonionic surfactant etc..If in the range of the effect without prejudice to the present invention, These and can also use two or more with a kind of exclusive use.As amphoteric surfactant, 2- alkyl-N- carboxylic first can be enumerated Base-N- hydroxyethyl imidazolines glycine betaine, coco-nut oil fatty acid amido propyl betaine, coconutalkyl alanine sodium, Lauryl amino dipropionic acid etc..As cationic surfactant, quaternary ammonium salt can be enumerated (for example, lauryl trimethyl chlorination Ammonium), higher amines halate (for example, hard tallow amine), haloalkylpyridin system (for example, chlorinated dodecane yl pyridines) etc.. As anion surfactant, alkyl sulfate salt, alkylaryl sulfonates, alkyl ether sulphate salts, alpha-olefin can be enumerated Sulfonate, alkylsulfonate, alkylbenzenesulfonate, alkylnaphthalene sulfonate, taurine system surfactant, methyl amimoacetic acid system surface are lived Property agent, isethionate system surfactant, N- acyl acidic amino acids system surfactant, alkylphosphonate, height Level soap and acylation polypeptide etc..As nonionic surfactant, the polyoxies such as polyoxyethylene ether can be enumerated Alkylidene alkyl ether；Polyoxyethylene phenyl ether；Polyether polyols derivative；Polyoxyethylene amine, polyoxy Ethylidene fatty acid amide, polyoxyethylene aliphatic acid diphenyl ether, polyoxyethylene fatty acid ester, polyoxyethylene dehydration mountain The polyoxyethylene derivative such as pears sugar alcohol fatty acid ester；Mono-fatty acid glyceride；Polyglyceryl fatty acid ester；Sorbitan alcohol ester Fat acid esters；Sucrose fatty ester；Polyoxyethylene castor oil；Polyoxyethylene hardened castor oil etc..For example, above-mentioned either table The carbon number of the alkyl of face activating agent can be 6~20 or 8~18.

It is expressed as follows using the dissolving reaction of the glass of hydrofluoric acid.

SiO₂+6HF→2H₂O+H₂SiF₆

Etching speed accelerates if hydrofluoric acid concentration is improved, if but etching speed it is too fast can not fully keep up with ultrasonic wave photograph The flowing for the product that the etching solution and etching tape of fine hole or inside grooves caused by penetrating promotes.

Hydrofluoric acid concentration contained by etching solution is the mass % of 0.05 mass %~8.0, from the erosion eliminated using ultrasonic irradiation In the substrate surface of fine hole or groove and the difference of the internal etching carried out in quarter, it is big that fine and gradient can be formed Deep hole or the point of groove set out, be preferably the matter of the mass %, more preferably 0.20 mass % of 0.10 mass %~7.0~5.0 Measure %.By reducing hydrofluoric acid concentration, the gradient in formed hole can be improved, but lost if undue reduction hydrofluoric acid concentration Etching speed is slack-off, and treatment effeciency is unnecessarily deteriorated.

The fluoride and the solubility of silicofluoride produced in the etching of glass caused by hydrofluoric acid is relatively low, therefore easily stays The progress of etching is hindered in fine hole or inside grooves.

Etching solution includes the situation of hydrofluoric acid and the nitration mixture of more than a kind of the inorganic acid in nitric acid, hydrochloric acid and sulfuric acid Under, the ionization of nitric acid, hydrochloric acid and sulfuric acid causes H⁺Fully exist, so that Balance be moved to the left.Free F^-Become It is few, therefore the generation of fluoride and silicofluoride is suppressed, it can stably keep hole fine caused by ultrasonic irradiation Or the flowing of the product of the etching solution and etching tape of inside grooves.During the concentration of simple reduction hydrofluoric acid, it is possible to reduce trip From F^-, but etching also becomes difficult to carry out, therefore suppress free F by strong acid^-Generation it is preferable.If improve nitric acid, hydrochloric acid and Then etch-rate accelerates the concentration of sulfuric acid, but fine caused by ultrasonic irradiation can not be fully kept up with if etch-rate is too fast The flowing for the product that the etching solution and etching tape of hole or inside grooves are come promotes.

Improve wellability of the etching solution to glass by adding surfactant, can make etching solution come in and go out micropore or The inside of groove becomes easy.The removal of the dirt further obtained by surfactant, the weight for preventing particle and product The effect newly adhered to, can also keep the etching of hole fine caused by ultrasonic irradiation or inside grooves to carry out well.For The effect of decontamination is improved, the amount of surfactant can be increased, if but increasing and at most having the problem of blister band comes and flushing Trouble.Surfactant adds 5ppm with regard to that can obtain effect.

Inorganic acid (preferably nitric acid) concentration of more than a kind contained in nitric acid, hydrochloric acid and sulfuric acid is in etching solution The mass % of 2.0 mass %~16.0, in the etching using ultrasonic irradiation, from eliminating in fine hole or the substrate table of groove Face and the difference of the internal etching carried out, the point that can form the big deep hole of fine and gradient or groove set out, preferably For the mass % of the mass % of 2.5 mass %~15.0, more preferably 3.0 mass %~14.0.

The content (mass concentration) of surfactant contained by etching solution is 5ppm~1000ppm, is utilizing ultrasonic irradiation Etching in, from the difference eliminated in the substrate surface of fine hole or groove and the internal etching carried out, can be formed fine And set out in terms of the big deep hole of gradient or groove, preferably 10ppm~800ppm, more preferably 15ppm~ 600ppm.The content of surfactant can use such as high performance liquid chromatography (HPLC/High Performance Liquid Chromatography) measure.

The temperature of etching period and etching solution can make choice according to the shape in rotten portion, target machining shape.Need Illustrate, the temperature of etching solution when being etched by improving, can improve etching speed.In addition, etching speed can also lead to The composition of overetch liquid adjusts.In the manufacturing method of the present invention, etching speed is with the etching of the glass substrate beyond the portion that goes bad Speed represents, is not particularly limited, and is preferably 0.1~9.0 μm/min, more preferably 0.2~7.0 μm/min, further excellent Elect 0.5~6.0 μm/min as.Furthermore, it is possible to by etching condition come the diameter of control hole.

Etching period is related with the thickness of slab of glass plate, therefore is not particularly limited, and is preferably 30~180 minutes or so.For Adjustment etch-rate can change the temperature of etching solution, be preferably 5~45 DEG C or so, more preferably 15~40 DEG C or so.Can To process at a temperature of more than 45 DEG C, but the volatilization of etching solution is very fast therefore impracticable.Can also be at the temperature below 5 DEG C Processing, but it is unpractical that etch-rate, which becomes the situation of extremely slow temperature,.

The etching solution of the present invention can be obtained by the way that above-mentioned each component is mixed in a solvent.Solvent does not limit especially It is fixed, it is preferably water.

In the glass with fine structure obtained by the manufacturing method of the present invention, hole gradient is in the laser pulse plane of incidence In both (the first face) and its opposing face (the second face), from the high aspect of glacing flatness, it is preferably more than 80 degree, is more preferably More than 85 degree.Described in the embodiment of the assay method of hole gradient as be described hereinafter.In addition, obtained by the manufacturing method of the present invention The glass with fine structure in, opening diameter is preferably 20~110 μm, more preferably 25~100 μm, more preferably 30~ 95μm.Opening diameter can be calculated by the image used in the observation of hole gradient.

Embodiment

Then, enumerate embodiment and further specifically describe the present invention, but the present invention and from any of these embodiments Limit, the people for having common knowledge in this area in the technological thought of the present invention can carry out various deformation.

[embodiment 1]

Using the glass substrate for the 30mm × 30mm × t0.52mm being made of the component of the glass sample 1 of table 1 below as examination Sample uses.

[table 1]

※ units are mole %

＜ goes bad portion formation process ＞

The high of Coherent company systems has been used to repeat solid pulse UV laser using the formation in the rotten portion of laser： AVIA355-4500.As the 3rd higher hamonic wave Nd：YVO₄Laser, repetition rate can obtain 6W or so most when being 25kHz Big laser power.The dominant wavelength of 3rd higher hamonic wave is 355nm.

The laser pulse projected by laser aid (pulse width 9ns, power 1.2W, beam diameter 3.5mm) is used into light beam Expander extends to 4 times, and the adjustable iris ring of scope used in 5~15mm of diameter cuts the light beam after the expansion Cut, optical axis is adjusted with galvanometer mirror, light beam is incident to the inside of glass plate using the f θ lens of focal length 100mm.Pass through Changing the size of aperture makes laser diameter change so that NA is changed to 0.020~0.075.At this time, converge to laser Leave the upper surface physical length only position of 0.15mm of glass plate.Make laser in a manner of radiation pulses are misaligned with 400mm/ The speed of second is scanned.

Laser light irradiation after, in the glass that sample is confirmed with light microscope, be irradiated with a laser be formed in part with The different rotten portion of other parts.Although each glass has differences, rotten portion is formed as a generally cylindrical, as shown in figure 3, Reach near the upper surface of glass near lower surface.

By repetition rate be set to 10~25kHz to sample irradiation laser.In addition, by changing on the thickness direction of glass Become focal position, the position (upper surface side or lower face side) in the rotten portion formed on glass is adjusted to most suitable.

Using the 1L containers of polyethylene as etching groove, using pure water as the ratio that solvent is recorded according to table 2 coordinate it is following into Divide so as to make etching solution.

The gloomy field chemical industry of hydrofluoric acid 46%

1.38 60% Northeast of nitric acid chemistry

High-performance nonionic surfactant NCW-1001 (30% aqueous solution of polyoxyalkylene alkyl ether) and light are pure Medicine industry

[table 2]

Component	Embodiment 1
		Hydrofluoric acid (quality %)	2.0
Nitric acid (quality %)	6.0
		Surfactant^※(ppm)	15

※ removes the component amount of solvent

Water is added into ultrasonic bath to defined water level, the etching solution for adding the component with table 2 is set wherein Etching groove, heating etching solution cause liquid temperature to reach 30 DEG C.Said sample (glass substrate) is stood on to the box made of vinyl chloride In and be put into etching groove, irradiate 40kHz, 0.26W/cm²Ultrasonic wave.Ultrasonic irradiation causes the temperature of etching solution to rise, because This exchanges the part water of ultrasonic bath to be kept for 30 DEG C ± 2 DEG C.Midway pull-up sample, etching speed is obtained by the change of substrate thickness Rate, determines etching period so as to implement to etch in a manner of substrate thickness at the end of etching is 440 μm, obtains with fine structure Glass.Sample obtained by pull-up, is fully rinsed with pure water, drying is allowed to hot wind.

The intensity of ultrasonic wave is set to output power (unit W) divided by floor space (the unit cm of etching groove²) obtained value.Make For ultrasonic bath, US-3R (model, output power 120W, frequency of oscillation 40kHz, AS ONE Co. Ltd. systems, groove ruler have been used It is very little：W303 × D152 × H150 (unit mm)).

Sample is cut off with glass cutting machine, and uses the grinding slice lapping section of #1000, #4000 successively.If etch at this time Rotten portion expose on section, then can not observe the profile of script, therefore adjust amount of grinding and be allowed to not expose.Surveyed as image Determine device, using CNC image measuring systems NexivVMR-6555 (model, Co., Ltd.'s Nikon systems, multiplying power 8, the visual field 0.58 × 0.44 (unit mm)), by the analyzer from cross-wise direction (thickness direction) sample, by focus be aligned to etching after hole Portion.By the angle being made of at 2 shown in 51a and 51b in each face of the analyzer measurement chart 4 substrate surface and hole side, And value is averaged as hole gradient.The hole gradient of the laser pulse plane of incidence (hereinafter referred to as " the first face ") is 86 degree, phase The hole gradient of reverse side (hereinafter referred to as " the second face ") is 86 degree.In addition, opening diameter is by the figure that is used in the observation of hole gradient As calculating.The image actually observed figure 5 illustrates.

As described in Example 1, by carrying out having used the present invention in the fine rotten portion that glass is formed and processing hole Etching solution ultrasonic irradiation etching, required hole (flat hole) fine, hole gradient is big and deep can be formed.

Cavitation erosion, vibration acceleration and current promotion etching solution that irradiation ultrasonic wave is brought and the product that etching tape comes disperse To the inside in fine hole.

The hydrofluoric acid concentration and concentration of nitric acid of etching solution are adjusted, is caused so as to adjust etching speed with keeping up with ultrasonic irradiation Fine hole etching solution and etching tape come product flowing promote.Nitric acid further suppresses to generate in fine hole Solubility low fluoride and silicofluoride, can stably keep the etching solution inside hole fine caused by ultrasonic irradiation The flowing of the product come with etching tape.

Surfactant makes etching solution improve the wellability of glass, becomes the inside of etching solution discrepancy micropore or groove Readily meanwhile, it is capable to prevent from being attached to inside the hole of product, and be maintained at micro- caused by ultrasonic irradiation well Thin hole or the progress of the etching of inside grooves.

Based on these reasons, the substrate surface in the etching of ultrasonic irradiation, eliminated in fine hole or groove is utilized The difference of the etching carried out with inside, can form hole (flat hole) fine, that gradient is big and deep.

As the variation of embodiment 1, as long as the structure that the glass used in ultrasonic irradiation etching has is etched in The rotten portion formed on glass and structure can obtain required shape, can penetrate through, it is possibility to have and bottom, can be hole, It can be groove.

On the frequency of oscillation of the ultrasonic wave of embodiment 1, multiple frequencies can be vibrated successively, can also be vibrated at the same time multiple Frequency, can also be modulated.

Hole gradient improves if the intensity of ultrasonic wave is improved, if improving the temperature of etching solution or improving hydrofluoric acid or choosing From the concentration of more than a kind inorganic acid in nitric acid, hydrochloric acid and sulfuric acid, then hole gradient is reduced rather than etching speed and accelerates.Can be with Ultrasonic intensity, etch temperature and etching solution match ratio are properly selected according to required gradient and processing speed.

As the variation of embodiment 1, usable hydrochloric acid or sulfuric acid replace the nitric acid coordinated in etching solution.

Can be beyond polyethylene as long as etching groove has patience to etching solution as the variation of embodiment 1 General-purpose plastics or engineering plastics, can be metals or to metal to improve the propagation efficiency of ultrasonic wave Implement the product of cladding.

As the variation of embodiment 1, in ultrasonic irradiation etching process, sample and ultrasonic irradiation direction can be made It is parallel, can also be vertical with ultrasonic irradiation direction, in order to reduce ultrasonic wave it is uneven caused by influence, examination can be shaken Sample, can also spinning sample.

[embodiment 2~6]

In addition to changing into the etching condition (etching solution forms and etching speed) shown in table 3, same as Example 1ly Ultrasonic irradiation etching is carried out, manufactures the glass with fine structure.The condition and evaluation result of etching are shown in table 3.

In embodiment 2~6, the thickness before the species of sample (glass substrate), the etching of sample and the thickness after etching Same as Example 1, the composition of etching solution is different from embodiment 1.

In embodiment 2, compared with the etching solution of embodiment 1, the hydrofluoric acid concentration of etching solution is reduced to 0.2 mass %, Concentration of nitric acid is increased into 14.0 mass %, and the content of surfactant is increased into 150ppm.In embodiment 3, embodiment 1 Etching solution compare, the hydrofluoric acid concentration of etching solution is increased into 5.0 mass %, and concentration of nitric acid is increased into 14.0 matter Measure %.The two has obtained the good through hole of more than 85 degree of hole gradient.

In addition, in embodiment 4, compared with the etching solution of embodiment 1, the concentration of nitric acid of etching solution is reduced to 3.0 matter % is measured, in embodiment 5, compared with the etching solution of embodiment 1, concentration of nitric acid is increased into 14.0 mass %, and by surface-active The content of agent increases to 150ppm.The two has obtained the good through hole of more than 85 degree of hole gradient.

Further in embodiment 6, surfactant is increased to relative to the content of the etching solution of embodiment 5 500ppm, as a result can obtain the good through hole of more than 85 degree of hole gradient.

[table 3]

※ removes the component amount of solvent

[embodiment 7~9]

In addition to changing into the etching condition (etching solution composition, ultrasonic irradiation condition and etching speed) shown in table 4, Ultrasonic irradiation etching is carried out same as Example 1ly, manufactures the glass with fine structure.The condition and evaluation result of etching exist Shown in table 4.

In embodiment 7~9, the thickness before the species of sample (glass substrate), the etching of sample and the thickness after etching It is same as Example 1.The composition of etching solution is identical in embodiment 7~9, and the condition of ultrasonic irradiation is respectively different.Embodiment 7 The ultrasonic wave of frequency of oscillation 28kHz is irradiated during middle etching process, the ultrasonic wave of frequency of oscillation 45kHz is irradiated in embodiment 8.The two It is a large amount of to produce cavitation erosion, obtain the good through hole (flat hole) of more than 85 degree of hole gradient.

As ultrasonic bath, W-113 (model, the output 100W, frequency of oscillation 28kHz/ of modifiable frequency of oscillation have been used 45kHz/100kHz, Honda Electronic's system, groove size：W240 × D140 × H100 (unit mm)).

The ultrasonic wave of frequency of oscillation 100kHz has been irradiated in embodiment 9.Cavitation erosion is nearly free from, and hole gradient is first Face is 81 degree, is 82 degree in the second face, and hole gradient reduces compared with the result implemented under the frequency of oscillation lower than this. Intensity by improving ultrasonic wave can improve hole gradient, therefore be beneficial for easily impaired sample, but than this The threshold value that the frequency of oscillation of higher produces cavitation erosion steeply rises therefore not preferred.

[comparative example 1]

The etching solution of surfactant, 0.5 mass % of hydrofluoric acid, 3.0 mass % of nitric acid are not being added in 30 DEG C of condition Under, sample (glass sample 1) same as Example 1 is stirred using blender without using ultrasonic wave, and etch with Reach substrate thickness same as Example 1.For the glass of gained, hole gradient is determined same as Example 1ly.Institute In the glass obtained, the first face of hole gradient is 76 degree, and the second face is 77 degree, and substantially there occurs closing waist in the hole of perforation.It is actual to see The image observed figure 6 illustrates.

[comparative example 2]

The etching solution of surfactant, 2.0 mass % of hydrofluoric acid, 3.0 mass % of nitric acid are not being added in 30 DEG C of condition Under, 40kHz, 0.26W/cm are irradiated to sample (glass sample 1) same as Example 1²Ultrasonic wave, be etched to hole and passed through Untill logical.For the glass of gained, hole gradient is determined same as Example 1ly.In the glass of gained, hole gradient First face is 72 degree, and the second face is 73 degree, and substantially there occurs closing waist in the hole of perforation.

[table 4]

※ removes the component amount of solvent

As described above, confirming the formation in the hole that can suppress low pitch by the manufacturing method of the present invention, obtain The glass with fine structure of the fine structures such as glacing flatness higher, deeper hole or groove is formd on the thickness direction of substrate.

[embodiment 10~12]

Using the glass substrate for the 30mm × 30mm × t0.52mm being made of the component of the glass sample 2~4 of table 1 as examination Sample uses.In addition to being changed to etching condition as shown in table 5, ultrasonic irradiation etching is carried out same as Example 1ly, is made The glass with fine structure is made.The condition and evaluation result of etching are is shown in table 5.Either case can obtain hole inclination The good through hole that more than 85 degree of degree.To the image that embodiment 12 as an example is observed figure 7 illustrates.

[table 5]

※ removes the component amount of solvent

[embodiment 13]

Nitric acid is replaced as inorganic acid, 2.0 matter of hydrofluoric acid using hydrochloric acid (35.0-37.0% aqueous solutions Northeast chemistry) Under conditions of 30 DEG C of etching solution for measuring %, 6.0 mass % of hydrochloric acid, surfactant 150ppm, to sample same as Example 1 Irradiate 40kHz, 0.26W/cm²Ultrasonic wave, be etched to hole perforation untill.Except be changed to the condition described in table 6 with Outside, the glass with fine structure has been obtained same as Example 1ly.In the glass of gained, the first face of hole gradient is 85 Degree, the second face are 88 degree, can obtain the good through hole of more than 85 degree of hole gradient.The condition and evaluation result of etching exist Shown in table 6.

[table 6]

※ removes the component amount of solvent

[embodiment 14]

The substrate of 30mm × 30mm × t0.50mm of synthetic quartz (SHIN-ETSU HANTOTAI's chemical industry) has been used as glass sample. Use femtosecond laser using the formation in the rotten portion of laser, export 6 μ J, 9 μm of processing department spot diameter Φ, pulse width 800fs, Repetition rate 2kHz, process velocity are irradiated under conditions of 0.2mm/ seconds.It can confirm that to have irradiated with light microscope and swash The rotten portion of about 10 μm of the diameter different from other parts or fine cavity are formd in the part of light.It was observed that image exist Shown in Fig. 8.

In addition to changing into the etching condition (etching solution composition, ultrasonic irradiation condition and etching speed) shown in table 7, Ultrasonic irradiation etching is carried out same as Example 1ly, manufactures the glass with fine structure.In the glass of gained, hole gradient The first face be 90 degree, the second face be 89 degree, substantially vertical through hole has been obtained in synthetic quartz.The condition of etching and comment Valency result is shown in table 7.Further, it was observed that image figure 9 illustrates.

[table 7]

※ removes the component amount of solvent

[comparative example 3]

It is right under conditions of 30 DEG C of the etching solution of hydrofluoric acid, 14.0 mass % of nitric acid, surfactant 150ppm is not added Sample irradiation 40kHz, 0.26W/cm same as Example 1²Ultrasonic wave.Even if implement 3 it is small when etching glass substrate Thickness does not also change, and also cannot get through hole.Being etched if not adding hydrofluoric acid to carry out, it is impossible to form hole in glass With the fine structure such as groove.

[comparative example 4]

It is right under conditions of 30 DEG C of the etching solution of nitric acid, 2.0 mass % of hydrofluoric acid, surfactant 150ppm is not added Sample irradiation 40kHz, 0.26W/cm same as Example 1²Ultrasonic wave, be etched to hole perforation untill.The glass of gained In glass, the first face of hole gradient is 78 degree, and the second face is 81 degree, cannot with the addition of such 80 degree of hole gradient during nitric acid Through hole above.

[comparative example 5]

Improving the erosion of concentration of nitric acid, 2.0 mass % of hydrofluoric acid, nitric acid 20.0 mass %, surfactant 150ppm Under conditions of carving 30 DEG C of liquid, 40kHz, 0.26W/cm are irradiated to sample same as Example 1²Ultrasonic wave, be etched to Untill hole penetrates through.In the glass of gained, the first face of hole gradient is 78 degree, and the second face is 79 degree, cannot get hole gradient For more than 80 degree through holes.

[table 8]

※ removes the component amount of solvent

Industrial applicibility

By the present invention the glass with fine structure manufacture method can be inhibited low pitch hole formation, Glacing flatness higher, the glass with fine structure formed with the fine structure such as deep hole or groove on the thickness direction of substrate.

Claims

1. a kind of manufacture method of the glass with fine structure, it has the etching work for irradiating ultrasonic wave to glass to be etched Sequence, etching solution used includes in the etching work procedure

Hydrofluoric acid,

More than a kind of the inorganic acid in nitric acid, hydrochloric acid and sulfuric acid, and

Surfactant；

In the etching solution, hydrofluoric acid concentration is the mass % of 0.05 mass %~8.0, inorganic acid concentration for 2.0 mass %~ 16.0 mass %, the content of surfactant is 5ppm~1000ppm.

2. the manufacture method of the glass according to claim 1 with fine structure, also has to glass before etching work procedure Glass irradiation laser pulse is so as to the process for forming rotten portion or processing hole.

3. the manufacture method of the glass according to claim 1 or 2 with fine structure, wherein, the vibration of ultrasonication Frequency is below 100kHz.

4. according to the manufacture method of the glass according to any one of claims 1 to 3 with fine structure, wherein, ultrasonic wave Intensity is 0.10W/cm²~5.0W/cm²。

5. the manufacture method of the glass according to any one of claims 1 to 4 with fine structure, wherein, inorganic acid is Nitric acid.

6. according to the manufacture method of the glass according to any one of claims 1 to 5 with fine structure, wherein, surface-active The content of agent is 10ppm~800ppm.

7. according to the manufacture method of the glass according to any one of claims 1 to 6 with fine structure, wherein, surface-active Agent is nonionic surfactant.

8. according to the manufacture method of the glass according to any one of claims 1 to 7 with fine structure, wherein, glass be containing There is TiOs of 0.1 mole of % less than 5.0 moles of %₂Glass with lower alkali content or alkali-free glass.

9. according to the manufacture method of the glass according to any one of claims 1 to 7 with fine structure, wherein, glass be containing There are the glass with lower alkali content or alkali-free glass of the CuO of 0.1 mole of more than % and 2.0 mole of below %.

10. the manufacture method of the glass according to any one of claims 1 to 9 with fine structure, wherein, after etching work procedure Fine structure is through hole in glass, and the angle of hole gradient is more than 80 degree.