KR102758493B1 - Thin film for substrate detachment and manufacturing method thereof - Google Patents

Abstract

According to the method for manufacturing a thin film for substrate detachment of the present invention, the method comprises the step of arranging a metal inorganic salt thin film layer made of a metal inorganic salt on one surface of a support substrate.

Description

Thin film for substrate detachment and manufacturing method thereof {Thin film for substrate detachment and manufacturing method thereof}

The present invention relates to a thin film for substrate detachment and a method for manufacturing the same.

As the information society develops, the demand for display devices for displaying images is increasing in various forms, and recently, various flat display devices such as liquid crystal display (LCD), plasma display panel (PDP), and organic light emitting diode (OLED) are being utilized.

Since these flat panel displays generally use glass substrates, they are inflexible, which limits their applications.

Accordingly, flexible display panels (FDPs, hereinafter, flexible panels) that are manufactured to be bendable by using flexible materials such as plastic and foil instead of glass substrates are being actively developed recently.

At this time, among the manufacturing processes of flexible panels, the process of manufacturing and handling thin film transistors (TFTs on Plastic: TOP) on a plastic substrate is an important process in the manufacturing process of flexible panels (flexible display panels: FDP). This is because it is difficult to directly manufacture thin film transistors on a plastic substrate due to the flexibility of the plastic substrate.

Accordingly, a thin film transistor is formed using a plastic substrate that is adhered or coated on a carrier substrate such as a glass substrate, and then the flexible panel is completed by detaching the carrier substrate from the plastic substrate.

The manufacturing process of a typical flexible panel is explained as follows: hydrogenated amorphous silicon (a-Si:H) is deposited on top of a carrier substrate, such as a glass substrate, to form a sacrificial layer. At this time, the hydrogenated amorphous silicon (a-Si:H) of the sacrificial layer is an inorganic material and is deposited on top of the carrier substrate through a PECVD (plasma enhanced chemical vapor deposition) process.

Then, an adhesive layer is formed on top of the sacrificial layer, a liquid plastic is coated on top of the adhesive layer, and then heat treatment is performed continuously to form a plastic substrate.

Afterwards, data wiring, gate wiring intersecting therewith, and an array layer of thin film transistors, etc. are formed on the upper part of the plastic substrate, thereby completing the flexible panel substrate.

Next, a laser beam of about 532 nm is irradiated on the back surface of the carrier substrate so that hydrogen gas is emitted from the hydrogenated amorphous silicon (a-Si:H) forming the sacrificial layer, thereby destroying the sacrificial layer. Accordingly, the plastic substrate on which the thin film transistor, etc. are formed is separated from the carrier substrate. At this time, a process of vacuum suction of the plastic substrate is performed in order to easily detach the plastic substrate from the carrier substrate.

However, the manufacturing process of such flexible panels has the problem of low production efficiency because the sacrificial layer is formed through a PECVD process that has complex process steps and takes a long time.

In addition, there is a problem that the product production yield is reduced because the array layer formed on top of the plastic substrate may be damaged by the laser beam.

In addition, there is a problem that the possibility of the array layer being damaged increases due to the process of vacuum suction on the upper part of the plastic substrate in order to detach the plastic substrate from the carrier substrate.

In particular, in order to detach and separate a plastic substrate from a carrier substrate, a laser beam is irradiated, but an expensive excimer laser detacher is used, and since the light source of this detacher has a limited lifespan, there is a disadvantage in that maintenance costs increase due to the need for continuous replacement.

In addition, since the laser light source width of the laser detachment device to be described above is narrow, such as 40 to 50 cm, it can only support up to the 6th generation substrate, so there is a limit to the size of the detachment area.

Republic of Korea 10-1033797 (2005.09.21) Republic of Korea 10-2019-0033078 (2019.03.28) Republic of Korea 10-2019-0119512 (2019.10.22)

The purpose of the present invention, which has been devised to solve the problems described above, is to provide a thin film for substrate detachment and a method for manufacturing the same, which can transmit light and heat energy using a long-life UV or IR lamp, has low maintenance costs, and can easily perform large-area substrate detachment of 11th generation glass or more by simply transmitting light and heat energy over a large area.

In addition, the purpose of the present invention is to provide a thin film for substrate detachment and a method for manufacturing the same, wherein the metal inorganic salt thin film layer for detachment is composed of a metal inorganic salt and metal oxide nanoparticles, the metal inorganic salt thin film layer is stable at a high temperature of 300°C or higher, has a low coefficient of thermal expansion, and outgassing occurs inside the metal inorganic salt thin film layer by stimulation of light and heat energy, or lattice parameter mismatch occurs between the metal inorganic salt thin film layer and the detachment bond layer, thereby facilitating detachment.

According to the method for manufacturing a thin film for substrate detachment of the present invention to achieve the above-mentioned purpose, the method comprises the step of arranging a metal inorganic salt thin film layer made of a metal inorganic salt on one surface of a support substrate.

In addition, the metal-inorganic salt thin film layer emits oxide gas to the outside when irradiated with light energy.

In addition, the metal inorganic salt thin film layer includes metal cations, anions and metal oxide nanoparticles, and the step of forming the metal inorganic salt thin film layer includes the step of coating and heat-treating an inorganic binder in which the metal oxide nanoparticles are dispersed on one surface of the support substrate to form a nanoparticle film; and the step of forming a metal inorganic salt thin film in which the metal cations and anions are combined.

In addition, the step of forming a metal-inorganic salt thin film in which the metal cation and anion are combined is performed by reacting a precursor of the metal cation with an oxide gas and oxygen or ozone and performing a heat treatment.

In addition, the metal cation includes one of Li, Be, Na, Mg, Al, K, Ca, Ti, V, Cr, Mn, Fe, Ni, Cu, Zn, Ga, Y, Zr, Nb, Mo, Ru, Pd, Ag, In, Sn, Cs, Ba, Hf, Ta, W, Re, Os, Pt, Au, and the anion includes one of carbonate (CO ₃ ^2- ), sulfonate (SO ₄ ^2- ), and nitrate (NO ₃ ^- ).

In addition, the metal oxide nanoparticles include one of TiO ₂ , ZnO, WO ₃ , CdSe, Fe ₂ O ₃ , Bi ₂ WO ₆ , BiVO ₄ , CdS, TaNO, Cu ₂ O, and CuO.

Additionally, the metal oxide nanoparticles have an optical band gap of 1.0 to 4.0 eV.

In addition, the invention further includes a step of forming a desorption assisting layer on at least one of one surface of the metal-inorganic salt thin film layer and the other surface of the metal-inorganic salt thin film layer.

In addition, the detachment-assisting layer is a metal thin film made of any one of Al, Ti, Fe, Ni, Cu, Mo, and Ag, or a thermally conductive thin film made of any one of graphene, graphite, and carbon nanotubes. A method for manufacturing a thin film for substrate detachment.

In addition, according to the substrate detachment thin film of the present invention for achieving the above-mentioned purpose, it includes: a support substrate; and a metal inorganic salt thin film layer formed of a metal inorganic salt and arranged on one surface of the support substrate; wherein the metal inorganic salt thin film layer emits oxide gas to the outside when irradiated with light energy.

Additionally, the metal-inorganic salt thin film layer includes metal cations, anions, and metal oxide nanoparticles.

In addition, the invention further includes a desorption assisting layer disposed on one surface of the metal-inorganic salt thin film layer or the other surface of the metal-inorganic salt thin film layer.

The effect of the present invention as described above is that it is possible to transmit light and heat energy using a long-life UV or IR lamp, thereby reducing maintenance costs, and can easily perform large-area substrate detachment of 11th generation glass or more by simply transmitting light and heat energy over a large area, thereby providing a thin film for substrate detachment and a method for manufacturing the same.

In addition, the effect of the present invention is that the metal inorganic salt thin film layer for desorption is composed of a metal inorganic salt and metal oxide nanoparticles, the metal inorganic salt thin film layer is stable at a high temperature of 300°C or higher, has a low coefficient of thermal expansion, and can provide a thin film for substrate desorption and a method for manufacturing the same, in which outgassing occurs inside the metal inorganic salt thin film layer by stimulation of light and heat energy, or lattice parameter mismatch occurs between the metal inorganic salt thin film layer and the desorption bond layer, facilitating desorption.

FIG. 1 is a flow chart showing a method for manufacturing a thin film for substrate detachment according to a preferred first embodiment of the present invention.
Figure 2 is a diagram showing the thermal decomposition characteristics, outgassing characteristics, and optimal mixing composition of non-hydrated metal inorganic salts according to compounds in which metal cations are combined in multiple ways.
Figure 3 is a diagram showing the optical band gap of metal compound nanoparticles.
Figure 4 is a drawing showing a method for manufacturing an inorganic binder including TiO ₂ among metal oxide nanoparticles using a sol-gel method.
Figure 5 is a drawing showing a method for forming a film of an inorganic binder with TiO ₂ , a metal oxide nanoparticle, dispersed on one side of a supporting substrate.
Figure 6 is a drawing showing the formation of a metal-inorganic salt thin film by reacting a metal cation precursor with _CO2 and ozone using atomic layer deposition.
Figure 7 (a) shows data for a thermogravimetric analyzer, and (b) shows data for a differential scanning calorimeter.
Figures 8 (a), (b), and (c) are diagrams showing topology, XRD, and FT-IR data, respectively, for a CaCO ₃ thin film formed using atomic layer deposition.
Figure 9 is a diagram showing an ^outgassing reaction _in which gases such as CO _x , SO _x , and _NO x are generated when light energy is irradiated on a metal-inorganic salt thin film layer containing anions of carbonate (CO ₃ ^2- ), sulfonate (SO 4 2- ), and nitrate (NO ₃ ^- ).
Figure 10 is a drawing showing the mechanism by which outgassing of a metal-inorganic salt thin film layer occurs.
FIG. 11 is a drawing showing a substrate detachment thin film manufactured using a method for manufacturing a substrate detachment thin film according to a second embodiment of the present invention.
FIG. 12 is a drawing showing a substrate detachment thin film manufactured using a method for manufacturing a substrate detachment thin film according to a third embodiment of the present invention.
FIG. 13 is a drawing showing a state of manufacturing a thin film for substrate detachment using a method for manufacturing a thin film for substrate detachment according to a third embodiment of the present invention.

The advantages and features of the present invention, and the methods for achieving them, will become clearer with reference to the embodiments described in detail below together with the accompanying drawings. However, the present invention is not limited to the embodiments disclosed below, but may be implemented in various different forms, and the present embodiments are provided only to make the disclosure of the present invention complete and to fully inform those skilled in the art of the scope of the invention, and the present invention is defined only by the scope of the claims. Like reference numerals refer to like elements throughout the specification.

Hereinafter, the present invention will be described with reference to drawings for explaining a thin film for substrate detachment and a method for manufacturing the same according to embodiments of the present invention.

A method for manufacturing a thin film for substrate detachment according to a first embodiment of the present invention may include a step (S10) of preparing a support substrate (10); a step (S20) of forming a metal inorganic salt thin film layer (20) made of a metal inorganic salt on one surface of the support substrate (10); a step (S30) of forming a flexible substrate (30) on one surface of the metal inorganic salt thin film layer (20); and a step (S50) of irradiating the other surface of the support substrate (10) with light energy to separate the metal inorganic salt thin film layer (20) and the flexible substrate (30). At this time, after the step (S30) of forming the flexible substrate (30) on one surface of the metal inorganic salt thin film layer (20), a step (S40) of forming a display panel (40) on one surface of the flexible substrate (30) may be further included.

Referring to Fig. 1, a step (S10) of preparing a support substrate (10) can be performed first.

In one embodiment of the present invention, the support substrate (10) may be formed of various materials such as glass or metal having sufficient rigidity.

For example, the support substrate (10) may include a glass material. Since the flexible substrate (30) itself has a flexible characteristic, the support substrate (10) may play a role in supporting the flexible substrate (30) while a display panel (40) including a thin film transistor and an organic light-emitting diode is formed on the flexible substrate (30).

After the step (S10) of preparing a support substrate (10), a step (S20) of forming a metal inorganic salt thin film layer (20) made of a metal inorganic salt on one surface of the support substrate (10) can be performed.

Here, it is preferable that one side located in one direction is the upper side. In addition, it is preferable that the other side located in the other direction, which will be described later, is the lower side.

The metal-inorganic salt thin film layer (20) may include metal cations, anions, and metal oxide nanoparticles.

At this time, the metal cation can be any one of Li, Be, Na, Mg, Al, K, Ca, Ti, V, Cr, Mn, Fe, Ni, Cu, Zn, Ga, Y, Zr, Nb, Mo, Ru, Pd, Ag, In, Sn, Cs, Ba, Hf, Ta, W, Re, Os, Pt, and Au.

In addition, the anion may be any one of carbonate (CO ₃ ^2- ), sulfonate (SO ₄ ^2- ), and nitrate (NO ₃ ^- ). These anions are effective in generating gases such as CO _X , SO _X , and NO _{X for outgassing. In addition, as detachment of the flexible substrate (30) from the metal inorganic salt thin film layer (20) occurs due to outgassing caused by the generation of gases such as CO X , SO X , and NO X , the surface} roughness of the outer surface can be made smaller than 6 nm.

Here, the metal-inorganic salt may be a compound composed of a combination of metal cations and anions.

For example, examples of metal carbonates include CaCO ₃ , MgCO ₃ , BaCO ₃ , Al ₂ (CO ₃ ) ₃ , Ti(CO ₃ ) ₂ , NiCO ₃ , SnCO ₃ , Sn(CO ₃ ) ₂ , PtCO ₃ , etc. In addition, examples of metal sulfonates include CaSO ₄ , MgSO ₄ , CuSO ₄ , SnSO ₄ , MnSO ₄ , FeSO ₄ , etc. In addition, examples of metal nitrates include Ca(NO ₃ ) ₂ , Ti(NO ₃ ) ₄ , Zn(NO ₃ ) ₂ , In(NO ₃ ) ₃ , AgNO ₃ , Ga(NO ₃ ) ₃ , etc.

In particular, the metal inorganic salt can also be composed of a combination of two or more metal cations. At this time, referring to FIG. 2, the non-hydrated metal inorganic salt thermal decomposition characteristics, outgassing characteristics, and mixing optimum composition according to the compound in which the metal cations are combined in multiple ways can be examined. Accordingly, a low CTE (coefficient of thermal expansion) and high heat-resistant metal inorganic salt thin film layer (20) can be formed.

In addition, the metal-inorganic salt may be formed in the form of a hydrate combined with water, but is not limited thereto.

The metal oxide nanoparticles can be any one of TiO ₂ , ZnO, WO ₃ , CdSe, Fe ₂ O ₃ , Bi ₂ WO ₆ , BiVO ₄ , CdS, TaNO, Cu ₂ O, CuO, and Si.

Additionally, the metal oxide nanoparticles may have an optical band gap of 1.0 to 4.0 eV, as shown in FIG. 3.

At this time, it may be desirable for the metal oxide nanoparticles to be stable to strong UV, have excellent charge transfer efficiency, be inexpensive, and be non-toxic, but the present invention is not limited thereto.

Metal oxide nanoparticles that can satisfy these conditions are used, preferably one of TiO ₂ , ZnO, WO ₃ , and Bi ₂ WO ₆ having an optical band gap close to 3 eV, but are not limited thereto.

Additionally, the size of metal oxide nanoparticles can range from several hundred um to several tens of nm.

These metal oxide nanoparticles can provide electrons or holes (positive holes) to the metal inorganic salt thin film layer (20) through photocatalytic charge transfer from light energy (lamp), thereby generating gases such as CO _X , SO _X , and NO _X at low temperatures. At this time, the flexible substrate (30) can be detached from the metal inorganic salt thin film layer (20) by the generated gas.

Specifically, the step (S20) of forming a metal-inorganic salt thin film layer (20) can be performed by coating and heat-treating an inorganic binder (21) in which metal oxide nanoparticles are dispersed on one surface of a support substrate (10) using a vacuum film-forming method such as atomic layer deposition, chemical vapor deposition, or sputtering to form a film of nanoparticles, and forming a metal-inorganic salt thin film (22) in which metal cations and anions are combined.

First, in the step of forming a nanoparticle film, an inorganic binder (21) in which metal oxide nanoparticles are dispersed is coated on one surface of a support substrate (10).

The inorganic binder (21) can be manufactured using metal oxide nanoparticles using a sol-gel method.

For example, referring to FIG. 4, an inorganic binder (21) including TiO ₂ among metal oxide nanoparticles can be manufactured by a sol-gel method.

In addition, when coating an inorganic binder (21) having metal oxide nanoparticles dispersed therein on one surface of a supporting substrate (10), one of spray coating, dip coating, spin coating, screen coating, offset printing, inkjet printing, pad printing, knife coating, kiss coating, gravure coating, brushing, ultrasonic micro-grinding spray coating, and spray-mist spray coating may be used.

And, referring to Fig. 5, a step of forming a film of nanoparticles by coating and heat-treating an inorganic binder (21) in which TiO ₂ among metal oxide nanoparticles is dispersed on one surface of a support substrate (10) can be examined. At this time, the heat treatment can be performed at 400°C.

The step of forming a metal inorganic salt thin film (22) in which metal cations and anions are combined can be performed by reacting a metal cation precursor with one of CO, CO ₂ , SO ₃ , NO, NO ₂ gas and oxygen or ozone using an atomic layer deposition method and performing a heat treatment.

Additionally, the metal cation precursor may be composed of any one of Diethylzinc (DEZ), Mg (Cp) ₂ , and Ca (thd) ₂ . In this case, Ca (thd) ₂ is calcium bis (2,2,6,6-tetramethylheptan-3,5-dione).

For example, referring to FIG. 6, it can be observed that a metal inorganic salt thin film (22) is formed by reacting the above-described metal cation precursor with CO ₂ and ozone using the atomic layer deposition method.

At this time, a plasma method may be used to provide a large amount of ionic active species, radicals, etc. by using a metal cation precursor, a gas such as CO, CO ₂ , SO ₃ , NO, NO _{2 ,} and oxygen or ozone as a reactant, to form a metal-inorganic salt film using an atomic layer deposition method, a chemical vapor deposition method, a sputtering method, etc.

And, referring to Fig. 7, the thermal stability and thermal decomposition of the metal-inorganic salt thin film (22) made of the metal-inorganic salt can be examined through a thermogravimetric analyzer (TGA) and a differential scanning calorimeter (DSC). Accordingly, the CTE (coefficient of thermal expansion) can be lowered to less than 20 ppm℃. Fig. 7 (a) is data for the thermogravimetric analyzer, and (b) is data for the differential scanning calorimeter.

Also, referring to Fig. 8, the topology, XRD, and FT-IR of the CaCO ₃ thin film formed using the atomic layer deposition method can be examined.

Meanwhile, the precursor of the metal cation can be a metal compound containing an organic ligand or a halogenated metal compound. The metal compound containing an organic ligand is a general term for a precursor used in a general atomic layer deposition method or chemical vapor deposition method.

And, specific examples of the organic ligand of the metal cation precursor may include various organic compounds such as alkyl groups such as methyl, ethyl, and propyl, alkoxy groups such as methoxy, ethoxy, and propoxy, alkylamino groups, and beta-diketones.

Meanwhile, by adding a small amount of organic matter or halogen compound in addition to the metal inorganic salt to the metal inorganic salt thin film layer (20), the adhesion of the formed metal inorganic salt thin film layer (20) can be improved.

Next, a step (S30) of forming a flexible substrate (30) on one surface of a metal-inorganic salt thin film layer (20) can be performed.

At this time, the flexible substrate (30) may include at least one material selected from the group consisting of polyethersulfone, polyacrylate, polyether imide, polyethylene naphthalate, polyethylene terephthalate, polyphenylene sulfide, polyarylate, polyimide, polycarbonate, or cellulose acetate propionate.

For example, a flexible substrate (30) can be formed by spin-coating a polyimide solution in the form of a varnish on one surface of a metal-inorganic salt thin film layer (20), and then hardening it through heat treatment.

And, a display panel (40) can be formed on one side of the flexible substrate (30). At this time, the display panel can include a thin film transistor and an organic light-emitting diode.

Finally, a step (S50) is performed to separate the metal-inorganic salt thin film layer (20) and the flexible substrate (30) by irradiating the other surface of the support substrate (10) with light energy. Here, the separation time can be within 180 seconds.

At this time, when light energy is irradiated on the other side of the support substrate (10), one of CO _X , SO _X , and NO _X gases is generated in the metal-inorganic salt thin film layer (20), and the interface between the metal-inorganic salt thin film layer (20) and the flexible substrate (30) is separated.

Here, the light energy may be UV, visible light, infrared light, etc., or heat may be applied during the light irradiation. In addition, the light irradiation may be applied with a flash lamp. In addition, the wavelength of the light irradiation may be 350 to 420 nm to maximize light efficiency, and since a wavelength less than 350 nm does not smoothly penetrate the support substrate (10), it is preferable to irradiate a wavelength of 350 nm or more, and a wavelength of 420 nm or more may also be irradiated within a range that does not affect the display panel (40).

For example, when light energy is applied to a substrate detachment thin film manufactured by the above-described method for manufacturing a substrate detachment thin film, as shown in FIG. 9, the metal inorganic salt thin film layer (20) contains anions such as carbonate (CO ₃ ^2- ), sulfonate (SO ₄ ^2- ), and nitrate (NO ₃ ^- ), so that outgassing that generates gases (23) such as CO, CO ₂ , SO ₃ , NO, and NO ₂ can occur.

Referring to Figure 10, the mechanism by which outgassing of the metal-inorganic salt thin film layer (20) occurs can be examined.

In addition to the above, the coefficient of thermal expansion (CTE) can be further improved to 10 ppm/℃ or less by increasing the adhesion of the metal inorganic salt thin film layer (20) to one surface of the support substrate (10). In addition, the film formation uniformity of the metal inorganic salt thin film layer (20) can be secured to 7% or less, and the process heat resistance can also be 350℃ or more.

Meanwhile, a method for manufacturing a thin film for substrate detachment according to a second embodiment of the present invention may include, with reference to FIG. 11, a step of preparing a support substrate (10); a step of forming a detachment-assisting layer (50) on one surface of the support substrate (10); a step of forming a metal-inorganic salt thin film layer (20) made of a metal-inorganic salt on one surface of the detachment-assisting layer (50); a step of forming a flexible substrate (30) on one surface of the metal-inorganic salt thin film layer (20); and a step of irradiating the other surface of the support substrate (10) with light energy to separate the metal-inorganic salt thin film layer (20) and the flexible substrate (30).

In addition, a method for manufacturing a thin film for substrate detachment according to a third embodiment of the present invention may include, with reference to FIG. 12, a step of preparing a support substrate (10); a step of forming a metal inorganic salt thin film layer (20) made of a metal inorganic salt on one surface of the support substrate (10); a step of forming a detachment auxiliary layer (50) on one surface of the metal inorganic salt thin film layer (20); a step of forming a flexible substrate (30) on one surface of the detachment auxiliary layer (50); and a step of irradiating the other surface of the support substrate (10) with light energy to separate the metal inorganic salt thin film layer (20) and the flexible substrate (30).

That is, the second and third embodiments described above are the same as the first embodiment, but may further include a step of forming a detachment assistance layer (50) between the support substrate (10) and the metal inorganic salt thin film layer (20) or between the metal inorganic salt thin film layer (20) and the flexible substrate (30).

This detachment-assisting layer (50) can smoothly transmit light energy stimulation to the metal-inorganic salt thin film layer (20) when light energy is applied. In addition, the detachment-assisting layer (50) can act as a gas barrier so that separation, i.e. detachment, by gas (23) generated from the metal-inorganic salt thin film layer (20) can easily occur.

In addition, in order to maximize the desorption effect due to outgassing between the metal-inorganic salt thin film layer (20) and the desorption assist layer (50) and the desorption effect due to lattice mismatch, the desorption assist layer (50) may use a metal, a carbon compound, a metal oxide, a metal nitride oxide, SiOx, SiNx, etc.

Here, as the size of the metal oxide nanoparticles, the plastic density, and the film flatness of the metal inorganic salt thin film layer (20) are improved, the surface roughness after desorption can be reduced to 4 nm or less.

At this time, the detachment assistance layer (50) may be a metal thin film made of any one of Al, Ti, Fe, Ni, Cu, Mo, and Ag, or a thermally conductive thin film made of any one of graphene, graphite, and carbon nanotubes.

And, the step of forming the detachable auxiliary layer (50) can be performed by hardening a metal thin film or a thermally conductive thin film through heat treatment via sputtering.

A method for manufacturing a thin film for substrate detachment according to the third embodiment described above is described.

Referring to Fig. 13, first, to synthesize an inorganic binder (21) in which TiO ₂ particles were dispersed, Tetraethylorthosilicate (TEOS) and Glycidoxpropyltrimethoxysilane (GPTS) were mixed in H ₂ O containing EtOH and HCl, and TiO ₂ particles were dispersed therein.

Then, an inorganic binder (21) having TiO ₂ particles dispersed therein was spray-coated on one surface of a support substrate (10) made of a glass substrate, and then heat-treated at 400°C.

Afterwards, a CaCO ₃ thin film (50 nm), which is a metal-inorganic salt thin film (22), was formed by heat treatment at 400°C using the atomic layer deposition method. At this time, calcium bis(2,2,6,6-tetramethylheptan-3,5-dione) [Ca(thd) ₂ ] was used as a metal precursor, and CO ₂ (100 sccm) and ozone (500 sccm) were used as reactants.

The atomic layer deposition process sequence was performed by repeating the cycle of Ca(thd) ₂ (1.0 s) injection - O ₃ (1.0 s) injection - CO ₂ (3.0 s) injection.

Next, a ZnO thin film was formed as a desorption assist layer (50) on one surface of the metal inorganic salt thin film layer (20) by sputtering.

Then, a polyimide solution in the form of varnish was spin-coated and then heat-treated at 350°C to harden it, thereby forming a flexible substrate (30).

Meanwhile, a substrate detachment film according to the present invention comprises a support substrate (10); a metal inorganic salt film layer (20) formed of a metal inorganic salt on one surface of the support substrate (10); and a flexible substrate (30) formed on one surface of the metal inorganic salt film layer (20). The film is characterized in that when light energy is irradiated on the other surface of the support substrate (10), the metal inorganic salt film layer (20) and the flexible substrate (30) are separated.

At this time, a detachment assistance layer (50) formed between the support substrate (10) and the metal-inorganic salt thin film layer (20) or between the metal-inorganic salt thin film layer (20) and the flexible substrate (30) may be further included.

Here, a detailed description of the thin film for substrate detachment is the same as Examples 1 to 3 of the method for manufacturing a thin film for substrate detachment described above, and therefore is omitted, and reference is made to the description of Examples 1 to 3 of the method for manufacturing a thin film for substrate detachment.

A person having ordinary skill in the art to which the present invention pertains will understand that the present invention can be implemented in other specific forms without changing the technical idea or essential characteristics thereof. Therefore, it should be understood that the embodiments described above are exemplary in all aspects and not restrictive. The scope of the present invention is indicated by the scope of the claims described below rather than the detailed description, and it should be interpreted that all changes or modified forms derived from the meaning and scope of the scope of the claims and the equivalent concepts thereof are included in the scope of the present invention. In addition, the operational order of the components described in the above-described process does not necessarily have to be performed in chronological order, and if the gist of the present invention is satisfied even if the execution order of each component and step is changed, such a process can fall within the scope of the rights of the present invention.

10: Supporting substrate
20: Metal-inorganic salt thin film layer
21: Weapon Binder
22: Metal-inorganic salt thin film
23 : Gas
30: Flexible substrate
40 : Display panel
50: Detachable auxiliary layer

Claims (12)

A step of arranging a metal-inorganic salt thin film layer made of a metal-inorganic salt on one surface of a support substrate; and
A step of forming a desorption assisting layer on at least one of the one surface of the metal inorganic salt thin film layer and the other surface of the metal inorganic salt thin film layer; comprising;
A method for manufacturing a thin film for substrate detachment, wherein the detachment-assisting layer comprises at least one of a metal, a metal oxide, a metal nitride oxide, a silicon oxide film, and a silicon nitride film.
In the first paragraph,
The above metal-inorganic salt thin film layer is a method for manufacturing a thin film for substrate detachment that releases oxide gas to the outside when irradiated with light energy.
In the second paragraph,
The above metal-inorganic salt thin film layer comprises metal cations, anions and metal oxide nanoparticles,
The step of forming the above metal-inorganic salt thin film layer is:
A step of coating and heat-treating an inorganic binder in which the metal oxide nanoparticles are dispersed on one surface of the support substrate to form a nanoparticle film; and
A method for manufacturing a thin film for substrate detachment, comprising a step of forming a metal inorganic salt thin film in which the above metal cations and anions are combined.
In the third paragraph,
The step of forming a metal-inorganic salt thin film in which the above metal cations and anions are combined is:
The precursor of the above metal cation is reacted with oxide gas and oxygen or ozone and then heat treated.
A method for manufacturing a thin film for substrate detachment.
In the third paragraph,
The above metal cations include any one of Li, Be, Na, Mg, Al, K, Ca, Ti, V, Cr, Mn, Fe, Ni, Cu, Zn, Ga, Y, Zr, Nb, Mo, Ru, Pd, Ag, In, Sn, Cs, Ba, Hf, Ta, W, Re, Os, Pt, and Au.
A method for manufacturing a thin film for substrate detachment, wherein the anion comprises any one of carbonate (CO ₃ ^2- ), sulfonate (SO ₄ ^2- ), and nitrate (NO ₃ ^- ).
In the third paragraph,
A method for manufacturing a thin film for substrate detachment, wherein the metal oxide nanoparticle comprises any one of TiO ₂ , ZnO, WO ₃ , CdSe, Fe ₂ O ₃ , Bi ₂ WO ₆ , BiVO ₄ , CdS, TaNO, Cu ₂ O, and CuO.
In Article 6,
The above metal oxide nanoparticles are a method for manufacturing a thin film for substrate detachment having an optical band gap of 1.0 to 4.0 eV.
In the second paragraph,
A method for manufacturing a substrate detachment film, wherein the metal-inorganic salt film layer is composed of a combination of two or more metal cations.
In the first paragraph,
The above-mentioned detachment-assisting layer is a method for manufacturing a thin film for substrate detachment, which is a metal thin film made of any one of Al, Ti, Fe, Ni, Cu, Mo, and Ag.
support substrate;
A metal inorganic salt thin film layer formed of a metal inorganic salt and arranged on one surface of the support substrate; and
Including a desorption auxiliary layer arranged on one surface of the metal inorganic salt thin film layer or the other surface of the metal inorganic salt thin film layer;
The above metal-inorganic salt thin film layer emits oxide gas to the outside when irradiated with light energy,
The above-mentioned detachment-assisting layer is a thin film for substrate detachment comprising at least one of a metal, a metal oxide, a metal nitride oxide, a silicon oxide film, and a silicon nitride film.
In Article 10,
The above metal-inorganic salt thin film layer is,
A thin film for substrate detachment comprising metal cations, anions and metal oxide nanoparticles.
In Article 10,
The above metal-inorganic salt thin film layer is a thin film for substrate detachment composed of a combination of two or more metal cations.