CN109750273A - A method for improving the stability of silver jewelry by coating based on atomic layer deposition - Google Patents
A method for improving the stability of silver jewelry by coating based on atomic layer deposition Download PDFInfo
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- CN109750273A CN109750273A CN201910074185.3A CN201910074185A CN109750273A CN 109750273 A CN109750273 A CN 109750273A CN 201910074185 A CN201910074185 A CN 201910074185A CN 109750273 A CN109750273 A CN 109750273A
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- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 title claims abstract description 152
- 229910052709 silver Inorganic materials 0.000 title claims abstract description 152
- 239000004332 silver Substances 0.000 title claims abstract description 152
- 238000000034 method Methods 0.000 title claims abstract description 87
- 238000000231 atomic layer deposition Methods 0.000 title claims abstract description 68
- 238000000576 coating method Methods 0.000 title abstract description 7
- 239000011248 coating agent Substances 0.000 title abstract description 6
- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical compound C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 claims abstract description 40
- 238000006243 chemical reaction Methods 0.000 claims abstract description 38
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 27
- 229910052593 corundum Inorganic materials 0.000 claims description 24
- 238000000151 deposition Methods 0.000 claims description 24
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 24
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 22
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 22
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 22
- 230000008021 deposition Effects 0.000 claims description 22
- 238000005352 clarification Methods 0.000 claims description 14
- 230000006872 improvement Effects 0.000 claims description 12
- 235000019441 ethanol Nutrition 0.000 claims description 11
- 229910052757 nitrogen Inorganic materials 0.000 claims description 11
- 239000012159 carrier gas Substances 0.000 claims description 7
- 230000004907 flux Effects 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 7
- 238000002791 soaking Methods 0.000 claims description 7
- 238000004140 cleaning Methods 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 2
- 239000010408 film Substances 0.000 abstract description 166
- 238000002845 discoloration Methods 0.000 abstract description 8
- 239000010409 thin film Substances 0.000 abstract description 5
- 229910018072 Al 2 O 3 Inorganic materials 0.000 abstract 1
- 230000003993 interaction Effects 0.000 abstract 1
- 238000004381 surface treatment Methods 0.000 abstract 1
- 239000000523 sample Substances 0.000 description 21
- 239000000758 substrate Substances 0.000 description 19
- 230000005540 biological transmission Effects 0.000 description 12
- 238000005260 corrosion Methods 0.000 description 12
- 230000007797 corrosion Effects 0.000 description 12
- 238000006748 scratching Methods 0.000 description 10
- 230000002393 scratching effect Effects 0.000 description 10
- 239000000463 material Substances 0.000 description 9
- 230000008569 process Effects 0.000 description 7
- 230000008859 change Effects 0.000 description 6
- 238000005259 measurement Methods 0.000 description 6
- 238000007747 plating Methods 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 230000007423 decrease Effects 0.000 description 5
- 230000003287 optical effect Effects 0.000 description 5
- 239000011734 sodium Substances 0.000 description 4
- 238000005494 tarnishing Methods 0.000 description 4
- 238000002834 transmittance Methods 0.000 description 4
- 230000010534 mechanism of action Effects 0.000 description 3
- 239000012528 membrane Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 229910018516 Al—O Inorganic materials 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 229910003460 diamond Inorganic materials 0.000 description 2
- 239000010432 diamond Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000003628 erosive effect Effects 0.000 description 2
- 230000003678 scratch resistant effect Effects 0.000 description 2
- 230000003068 static effect Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- MKYBYDHXWVHEJW-UHFFFAOYSA-N N-[1-oxo-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propan-2-yl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(C(C)NC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 MKYBYDHXWVHEJW-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000005357 flat glass Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 238000007373 indentation Methods 0.000 description 1
- 230000002452 interceptive effect Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 229910021421 monocrystalline silicon Inorganic materials 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 238000000879 optical micrograph Methods 0.000 description 1
- 238000000399 optical microscopy Methods 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000013074 reference sample Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 229910052594 sapphire Inorganic materials 0.000 description 1
- 239000010980 sapphire Substances 0.000 description 1
- 238000001338 self-assembly Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 229910052979 sodium sulfide Inorganic materials 0.000 description 1
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000005486 sulfidation Methods 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
Landscapes
- Other Surface Treatments For Metallic Materials (AREA)
- Physical Vapour Deposition (AREA)
Abstract
本发明属于银饰品表面处理技术领域，具体涉及一种基于原子层沉积法进行镀膜改善银饰品稳定性的方法。本发明所述改善银饰品稳定性的方法，是基于原子层沉积法，以三甲基铝和水为反应源，对银饰表面进行Al2O3薄膜的沉积镀膜，以赋予银饰高硬度和强化学惰性，改善银饰品的稳定性；并通过对镀膜银饰的色差、耐划擦、和抗变色性能之间的交互关系的研究，获得了镀膜的最佳厚度值，以获得最佳的薄膜透明度和耐划擦、抗变色性能，解决了现有技术中镀膜方法无法同时满足银饰品的光泽质感和耐划擦、抗变色性能的问题。
The invention belongs to the technical field of surface treatment of silver ornaments, and in particular relates to a method for improving the stability of silver ornaments by coating based on an atomic layer deposition method. The method for improving the stability of silver ornaments of the present invention is based on atomic layer deposition, using trimethyl aluminum and water as reaction sources to deposit and coat the surface of silver ornaments with Al 2 O 3 thin film, so as to impart high hardness and strength to silver ornaments. Chemically inert, improving the stability of silver jewelry; and through the study of the interaction between the color difference, scratch resistance, and discoloration resistance of coated silver jewelry, the optimal thickness value of the coating was obtained to obtain the best film transparency. and scratch resistance and discoloration resistance, and solve the problem that the coating method in the prior art cannot satisfy the glossy texture, scratch resistance and discoloration resistance of silver jewelry at the same time.
Description
Technical field
The invention belongs to Silver Jewelry technical field of surface, and in particular to one kind carries out plated film based on atomic layer deposition method
Improve the method for Silver Jewelry stability.
Background technique
Silver Jewelry is a kind of ornaments made with metallic silver, has the characteristics that smooth texture, rich in gloss, easy moulding, by
To the extensive favor in market, according to statistics, 925 silver jeweleries whole world year silver consuming amount is more than five kilotons.But silver is especially sulphur in an atmosphere
Nature tarnishing easily occurs in the presence of in the case of leads to appearance degradation, and by the puzzlement intolerant to scratching and problem easy to change.
The specific requirement of marketization application of 925 plated film silver jeweleries specifically includes that keep the original metallic of 925 silver jeweleries
Sense, it is desirable that color difference≤2.5 before and after silver jeweleries plated film；And require plated film silver jeweleries in the sodium sulfide solution that concentration is 0.05mol/L,
Static corrosion 30min, without obvious metachromatism.In the prior art, the method for preventing Silver Jewelry tarnishing includes to silver products
The mode varnished, but due to interference or other optical changes, the coating layer thickness variation on silver products will lead to Silver Jewelry
Color change can destroy the visual effect of ornaments.
Due to having the characteristics that LBL self-assembly, using atomic layer deposition (ALD) in 925 silver jeweleries surface depositing ultrathin Al2O3
Film can assign silver jeweleries high rigidity and extensive chemical inertia.However, existing carry out plated film to Silver Jewelry using atomic layer deposition method
In method, in view of the reciprocal effect for needing to balance between the color difference for considering plated film silver jeweleries, resistance to scratching and discoloration-resisting, not yet look for
The resistance to scratching and anti-discoloration of Silver Jewelry is effectively ensured while retaining Silver Jewelry gloss texture to suitable plated film mode
Energy.
Summary of the invention
For this purpose, a kind of based on atomic layer deposition method progress plated film improvement technical problem to be solved by the present invention lies in providing
The method of Silver Jewelry stability can not meet the gloss texture of Silver Jewelry and scratch-resistant to solve film plating process in the prior art simultaneously
The problem of wiping, discoloration-resisting.
In order to solve the above technical problems, of the present invention a kind of based on atomic layer deposition method progress plated film improvement Silver Jewelry
The method of stability, including ultra-thin Al is synthesized in Silver Jewelry deposition based on atomic layer deposition method2O3The step of film, described in control
Al2O3The thickness d of film is > 0-40nm.
Preferably, described plated film is carried out based on atomic layer deposition method to improve the method for Silver Jewelry stability, described in control
Al2O3The thickness d of film is 10-30.5nm.
More preferably, described plated film is carried out based on atomic layer deposition method to improve the method for Silver Jewelry stability, described in control
Al2O3The thickness d of film is 24.8nm.
Specifically, the atomic layer deposition method carries out Al using trimethyl aluminium and water as reaction source2O3The deposition of film synthesizes.
Specifically, the reaction temperature of the atomic layer deposition method is 200 DEG C.
Specifically, the atomic layer deposition method specifically comprises the following steps:
(1) reaction chamber is opened, silver jeweleries sample to be deposited is placed on specimen holder, closes reaction chamber, and carry out vacuumizing place
Reason；
(2) heating mode is opened, set temperature is heated to；
(3) setting is following executes parameter: TMA burst length 1s, TMA soaking time 3s, TMA clarification time 70s, H2When O pulse
Between 1s, H2O clarification time 70s, set carrier gas flux 70sccm, 200 DEG C of growth temperature；And it executes program and carries out atomic layer deposition
Product；
(4) after above-mentioned deposition procedure, be vented and take out sample to get.
Preferably, the method also includes cleaning the Silver Jewelry surface using ethyl alcohol and acetone.
More preferably, the cleaning step carries out under ultrasonic conditions.
More preferably, further include the steps that drying up the Silver Jewelry after cleaning with high pure nitrogen.
The invention also discloses by the method system for carrying out plated film improvement Silver Jewelry stability based on atomic layer deposition method
The Silver Jewelry obtained.
The method of the present invention for improving Silver Jewelry stability is to be with trimethyl aluminium and water based on atomic layer deposition method
Reaction source carries out Al to silver jeweleries surface2O3The deposition plating of film improves silver jeweleries to assign silver jeweleries high rigidity and extensive chemical inertia
The stability of product；And by the research of the interactive relation between color difference, resistance to scratching and the discoloration-resisting to plated film silver jeweleries, obtain
The optimum thickness value for obtaining plated film solves the prior art to obtain optimal film clarity and resistance to scratching, discoloration-resisting
Middle film plating process can not meet the problem of gloss texture and resistance to scratching, discoloration-resisting of Silver Jewelry simultaneously.
Detailed description of the invention
In order to make the content of the present invention more clearly understood, it below according to specific embodiments of the present invention and combines
Attached drawing, the present invention is described in further detail, wherein
Fig. 1 is the element composition and phase structure of thickness 30nm film in experimental example 1, wherein (a) is x-ray photoelectron spectroscopy,
It (b) is X-ray diffraction spectrogram；
Fig. 2 is the comparison of the light transmission of different-thickness film and plating membrane sample color difference in experimental example 2 of the present invention, wherein (a) is
Five kinds of films of different-thickness are (b) color difference of plated film silver strip in the transmitted spectrum of visible region；
Fig. 3 is the optical microscope photograph in the embodiment of the present invention 3 after silver strip sample static corrosion 30min, wherein (a) is not
Plated film silver strip is (b) silver strip that coating film thickness is 10nm, (c) is the silver strip that coating film thickness is 15 nm；
Fig. 4 is the present invention with a thickness of the film of 100nm and the mechanical property of 925 silver medals, wherein (a) is nano hardness, (b) is bullet
Property modulus；
Fig. 5 is Al of the present invention2O3The mechanism of action of the film thickness to 925 silver strip comprehensive performance of plated film；
Fig. 6 is the structural schematic diagram of ALD equipment of the present invention；
Appended drawing reference indicates in figure are as follows: 1- mistress, 2- interior room, 3- heater, 4- tray rack, chamber lid in 5-.
Specific embodiment
ALD equipment structure chart as shown in FIG. 6 carries out the ALD of atomic layer deposition method operation in the following embodiments of the present invention
Equipment includes mistress 1, interior room 2, and the heater 3 being set between the mistress 1 and interior room 2, is arranged inside the interior room 2
There is the tray rack 4 for placing sample to be deposited, and is realized and sealed by the fastening of interior chamber lid 5 and the interior room 2.The heater 3
For the interior room 2 to be heated to set temperature.
Embodiment 1
Carrying out plated film based on atomic layer deposition method described in the present embodiment improves the method for Silver Jewelry stability, includes the following steps:
(1) taking 925 silver strip materials (10mm*10mm*2mm) is substrate, conventionally, carries out ultrasonic wave using ethyl alcohol and acetone
Substrate surface is cleaned, is then dried up with high pure nitrogen, it is spare；
(2) ALD equipment as shown in FIG. 6 is used, with trimethyl aluminium (TMA) He Shuiwei reaction source, controlling reaction temperature is 200 DEG C
It carries out deposition and synthesizes ultra-thin Al2O3Film:
Reaction chamber is opened, silver jeweleries sample to be deposited is placed on specimen holder, closes reaction chamber, and carry out vacuumize process；
Heating mode is opened, is heated to 200 DEG C of set temperature；
Setting is following to execute parameter: TMA burst length 1s, TMA soaking time 3s, TMA clarification time 70s, H2The O burst length
1s, H2O clarification time 70s, set carrier gas flux 70sccm, 200 DEG C of growth temperature；And it executes program and carries out atomic layer deposition；
After above-mentioned deposition procedure, it is vented and takes out sample, the ultra-thin Al is controlled by ellipsometer2O3The thickness of film
For 11.6nm to get.
Embodiment 2
Carrying out plated film based on atomic layer deposition method described in the present embodiment improves the method for Silver Jewelry stability, includes the following steps:
(1) taking 925 silver strip materials (10mm*10mm*2mm) is substrate, conventionally, carries out ultrasonic wave using ethyl alcohol and acetone
Substrate surface is cleaned, is then dried up with high pure nitrogen, it is spare；
(2) ALD equipment as shown in FIG. 6 is used, with trimethyl aluminium (TMA) He Shuiwei reaction source, controlling reaction temperature is 200 DEG C
It carries out deposition and synthesizes ultra-thin Al2O3Film:
Reaction chamber is opened, silver jeweleries sample to be deposited is placed on specimen holder, closes reaction chamber, and carry out vacuumize process；
Heating mode is opened, is heated to 200 DEG C of set temperature；
Setting is following to execute parameter: TMA burst length 1s, TMA soaking time 3s, TMA clarification time 70s, H2The O burst length
1s, H2O clarification time 70s, set carrier gas flux 70sccm, 200 DEG C of growth temperature；And it executes program and carries out atomic layer deposition；
After above-mentioned deposition procedure, it is vented and takes out sample, the ultra-thin Al is controlled by ellipsometer2O3The thickness of film
For 15.5nm to get.
Embodiment 3
Carrying out plated film based on atomic layer deposition method described in the present embodiment improves the method for Silver Jewelry stability, includes the following steps:
(1) taking 925 silver strip materials (10mm*10mm*2mm) is substrate, conventionally, carries out ultrasonic wave using ethyl alcohol and acetone
Substrate surface is cleaned, is then dried up with high pure nitrogen, it is spare；
(2) ALD equipment as shown in FIG. 6 is used, with trimethyl aluminium (TMA) He Shuiwei reaction source, controlling reaction temperature is 200 DEG C
It carries out deposition and synthesizes ultra-thin Al2O3Film:
Reaction chamber is opened, silver jeweleries sample to be deposited is placed on specimen holder, closes reaction chamber, and carry out vacuumize process；
Heating mode is opened, is heated to 200 DEG C of set temperature；
Setting is following to execute parameter: TMA burst length 1s, TMA soaking time 3s, TMA clarification time 70s, H2The O burst length
1s, H2O clarification time 70s, set carrier gas flux 70sccm, 200 DEG C of growth temperature；And it executes program and carries out atomic layer deposition；
After above-mentioned deposition procedure, it is vented and takes out sample, the ultra-thin Al is controlled by ellipsometer2O3The thickness of film
For 21.1nm to get.
Embodiment 4
Carrying out plated film based on atomic layer deposition method described in the present embodiment improves the method for Silver Jewelry stability, includes the following steps:
(1) taking 925 silver strip materials (10mm*10mm*2mm) is substrate, conventionally, carries out ultrasonic wave using ethyl alcohol and acetone
Substrate surface is cleaned, is then dried up with high pure nitrogen, it is spare；
(2) ALD equipment as shown in FIG. 6 is used, with trimethyl aluminium (TMA) He Shuiwei reaction source, controlling reaction temperature is 200 DEG C
It carries out deposition and synthesizes ultra-thin Al2O3Film:
Reaction chamber is opened, silver jeweleries sample to be deposited is placed on specimen holder, closes reaction chamber, and carry out vacuumize process；
Heating mode is opened, is heated to 200 DEG C of set temperature；
Setting is following to execute parameter: TMA burst length 1s, TMA soaking time 3s, TMA clarification time 70s, H2The O burst length
1s, H2O clarification time 70s, set carrier gas flux 70sccm, 200 DEG C of growth temperature；And it executes program and carries out atomic layer deposition；
After above-mentioned deposition procedure, it is vented and takes out sample, the ultra-thin Al is controlled by ellipsometer2O3The thickness of film
For 25.0nm to get.
Embodiment 5
Carrying out plated film based on atomic layer deposition method described in the present embodiment improves the method for Silver Jewelry stability, includes the following steps:
(1) taking 925 silver strip materials (10mm*10mm*2mm) is substrate, conventionally, carries out ultrasonic wave using ethyl alcohol and acetone
Substrate surface is cleaned, is then dried up with high pure nitrogen, it is spare；
(2) ALD equipment as shown in FIG. 6 is used, with trimethyl aluminium (TMA) He Shuiwei reaction source, controlling reaction temperature is 200 DEG C
It carries out deposition and synthesizes ultra-thin Al2O3Film:
Reaction chamber is opened, silver jeweleries sample to be deposited is placed on specimen holder, closes reaction chamber, and carry out vacuumize process；
Heating mode is opened, is heated to 200 DEG C of set temperature；
Setting is following to execute parameter: TMA burst length 1s, TMA soaking time 3s, TMA clarification time 70s, H2The O burst length
1s, H2O clarification time 70s, set carrier gas flux 70sccm, 200 DEG C of growth temperature；And it executes program and carries out atomic layer deposition；
After above-mentioned deposition procedure, it is vented and takes out sample, the ultra-thin Al is controlled by ellipsometer2O3The thickness of film
For 30.5nm to get.
Embodiment 6
Carrying out plated film based on atomic layer deposition method described in the present embodiment improves the method for Silver Jewelry stability, includes the following steps:
(1) taking 925 silver strip materials (10mm*10mm*2mm) is substrate, conventionally, carries out ultrasonic wave using ethyl alcohol and acetone
Substrate surface is cleaned, is then dried up with high pure nitrogen, it is spare；
(2) ALD equipment as shown in FIG. 6 is used, with trimethyl aluminium (TMA) He Shuiwei reaction source, controlling reaction temperature is 200 DEG C
It carries out deposition and synthesizes ultra-thin Al2O3Film (with embodiment 1) controls the ultra-thin Al by ellipsometer2O3Film with a thickness of
24.8nm to get.
Embodiment 7
Carrying out plated film based on atomic layer deposition method described in the present embodiment improves the method for Silver Jewelry stability, includes the following steps:
(1) taking 925 silver strip materials (10mm*10mm*2mm) is substrate, conventionally, carries out ultrasonic wave using ethyl alcohol and acetone
Substrate surface is cleaned, is then dried up with high pure nitrogen, it is spare；
(2) ALD equipment as shown in FIG. 6 is used, with trimethyl aluminium (TMA) He Shuiwei reaction source, controlling reaction temperature is 200 DEG C
It carries out deposition and synthesizes ultra-thin Al2O3Film (with embodiment 1) controls the ultra-thin Al by ellipsometer2O3Film with a thickness of
10nm to get.
Embodiment 8
Carrying out plated film based on atomic layer deposition method described in the present embodiment improves the method for Silver Jewelry stability, includes the following steps:
(1) taking 925 silver strip materials (10mm*10mm*2mm) is substrate, conventionally, carries out ultrasonic wave using ethyl alcohol and acetone
Substrate surface is cleaned, is then dried up with high pure nitrogen, it is spare；
(2) ALD equipment as shown in FIG. 6 is used, with trimethyl aluminium (TMA) He Shuiwei reaction source, controlling reaction temperature is 200 DEG C
It carries out deposition and synthesizes ultra-thin Al2O3Film (with embodiment 1) controls the ultra-thin Al by ellipsometer2O3Film with a thickness of
15nm to get.
Embodiment 9
Carrying out plated film based on atomic layer deposition method described in the present embodiment improves the method for Silver Jewelry stability, includes the following steps:
(1) taking 925 silver strip materials (10mm*10mm*2mm) is substrate, conventionally, carries out ultrasonic wave using ethyl alcohol and acetone
Substrate surface is cleaned, is then dried up with high pure nitrogen, it is spare；
(2) ALD equipment as shown in FIG. 6 is used, with trimethyl aluminium (TMA) He Shuiwei reaction source, controlling reaction temperature is 200 DEG C
It carries out deposition and synthesizes ultra-thin Al2O3Film (with embodiment 1) controls the ultra-thin Al by ellipsometer2O3Film with a thickness of
30nm to get.
Experimental example
In the following experimental examples of the present invention:
Influence using 925 silver strips measurement plated film to silver strip color difference and discoloration-resisting；
<100>face monocrystalline silicon piece and high light transmission sheet glass is utilized to measure the mechanical property and light transmission of film respectively；
Utilize the thickness of ellipsometer measurement film；
Utilize the phase structure of X-ray diffractometer characterization film；
Using spectrophotometer measurement film visible region light transmission (error 5%)；
Utilize the constituent of x-ray photoelectron spectroscopy characterization film；
Utilize the hardness and elastic modulus of nano-hardness tester measurement film and 925 silver medals；
Utilize the discoloration of silver strip after the corrosion of optical microphotograph sem observation；
Using the Lab value of silver strip before and after color difference meter measurement plated film, light source D65, standard observer's angle is CIE10o, with not
Plating membrane sample is reference, calculates the value of chromatism of plated film silver strip；
The discoloration-resisting that silver strip is checked using corrosion experiment, is placed on silver strip the Na of 0.05mol/L2In S etchant solution, corrosion
Time is 0.5h, and corrosion front and back is dried and weighed to sample.
1, the element composition and phase structure of film
The element composition and phase structure that 30nm thickness thin film silver jeweleries sample is deposited in embodiment 9, test are measured by ellipsometer
As a result as shown in Figure 1.
(a) has stable peak position, respectively it is found that the XPS spectrum of Al 2p and O 1s are symmetrical Gaussian Profile in Fig. 1
For 74.3eV and 531.3eV；The difference of the combination energy of O 1s and Al2p is 457.0eV, close to sapphire (pure Al2O3)
456.7eV shows that film is mainly made of Al-O key.
In Fig. 1 (b) it is found that the XRD spectra diffraction maximum position before and after silver strip plated film without significant change；It is Ag's
(111), (200), (220) and (311) crystal face characteristic peak shows that film is undefined structure.It follows that sinking in embodiment 9
Long-pending film is the Al of undefined structure2O3。
2, influence of the film thickness to plated film silver jeweleries color
In order to investigate influence of the film optical properties to plated film silver strip texture, deposition thickness in embodiment 1-5 is had detected respectively
The light transmission of film and the Lab value of plated film silver strip, the light transmission of film and chromatism test result such as Fig. 2 institute of plating membrane sample
Show.
The influence of film thickness and wavelength to transmissivity it can be seen from (a), increases with film thickness in Fig. 2, and transmissivity becomes in decline
Gesture.It is respectively 100%, 99.9%, 99.3%, 98.6% and 98.1% that thickness thin film average transmittance is made in embodiment 1-5.And
Transmittance graph line style is essentially identical, illustrates that film thickness influences less the optical transmission characteristics of film, and increase with wavelength, transmissivity
It is in rising trend.In Fig. 2 shown in (a), the transmittance graph of film is divided into 4 stages with dotted line: at 380nm, film
Transmissivity is minimum；First stage is 380nm to 400nm wave band, and transmissivity ramps, and the slope of curve is maximum；Second stage is
400nm linearly rises to 470nm wave band, transmissivity, and the slope of curve is taken second place；Phase III is 470nm to 550nm wave band, thoroughly
The rate ascendant trend of penetrating gradually slows down, and the slope of curve is gradually decrease to 0.There is maximum value at 550nm in transmissivity；Fourth stage is
550nm is in flat line to 760nm wave band, transmittance graph, and transmissivity is without significant change.It follows that film is in visible light wave
Section transmission be it is non-uniform, the transmissivity of 550nm to 760nm wave band is apparently higher than 380nm to 550nm wave band.
The color difference of thickness plated film silver strip, the value point in bracket is made it can be seen from (b) in embodiment 1-5 in Fig. 2
It is not L*、∆a*、∆b*.Value of chromatism is calculated by formula (1):
(1)
Refer in L*a*b*Standard deviation under the colour space, size can directly characterize human eye for the feeling of object color
Gap.∆L*, a*, b*The difference of lightness L* and chromaticity index a* and b* respectively between reference sample and sample.
Color difference increases with film thickness in the trend increased it can be seen from (b) in Fig. 2.Using non-plated film silver strip as reference, plated film
Color difference with a thickness of the silver strip of 11.6nm, 15.5nm, 21.1nm, 25.0nm, 30.5nm is respectively 0.46,1.1,1.78,2.61,
3.67.After quadratic fit curve, the critical film thickness for obtaining meeting color difference≤2.5 is 24.8nm.
Increase it can be seen from L, a, b variation in Fig. 2 in attached drawing bracket shown in (b) with film thickness, L value reduces, a value base
This is constant, and b value increases.L value reduces, and the brightness decline of plated film silver strip, reason is that film transmission increases with film thickness and declined.
A value is basically unchanged, and b value increases, and shows the inclined yellow of plated film silver strip color, it may be possible to uneven transmission of the film to visible light.
To sum up, the uneven transmission of film will lead to plated film silver jeweleries and generate color, and color increases with film thickness and deepened；It is thin
The average light transmission rate of film increases with film thickness and is declined, and plated film silver strip brightness is caused to decline.Color change and brightness decline cause
The color difference of plated film silver strip increases, and meeting the film thickness range that color difference≤2.5 require is 0-24.8 nm.
3, influence of the film thickness to plated film silver jeweleries anti-tarnishing ability
The test of plated film silver jeweleries anti-tarnishing ability, the optical microscopy after silver slice corrosion are carried out to silver strip made from embodiment 7-8
Photo is as shown in Fig. 3.
As Fig. 3 light microscopic and surrosion the results show that the discoloration-resisting of silver strip increases with film thickness and becomes strong.Fig. 3
In the non-plated film silver strip surface of (a) have the corrosion phenomenon of large area color burn, part is in dark brown, surrosion 0.0004g,
Show that sulfidation corrosion will lead to 925 silver medal serious discolorations；The silver strip of (b) has line style corrosion in Fig. 3, and rest part is existing without obvious discoloration
As surrosion 0.0002g shows that plated film can obviously improve the discoloration-resisting of 925 silver medals；The silver strip of (c) does not occur in Fig. 3
Metachromatism, the weight for corroding front and back is unchanged, and when showing film thickness >=15nm, plated film silver strip has withstood Na completely2S corrosion is molten
The erosion of liquid.
It is noted that dark and light two scratches in Fig. 3 shown in the yellow arrows of (b).Light scratch
It should be that silver surface and hard object scratching generate before plated film, taint-free reason may be the blanketing effect of 10nm film, ALD
Has the advantages that on complicated shape plating piece also uniform deposition film；Dark scratch may be silver surface and hard object stroke after plated film
It wipes and generates, the reason of discoloration may be the integrality that scratching destroys film, and exposed silver is corroded at scratch, but become
Color phenomenon is not spread around scratch, illustrates that adhesion of thin film is good.
It follows that film has the characteristics that adhesive force is good and it is uniform to cover, increase with coating film thickness, the resistance of silver strip
The enhancing of color ability.As film thickness >=15nm, plated film silver strip can keep out Na2The erosion of S etchant solution.
4, influence of the film thickness to plated film silver jeweleries mechanical property
This experimental example studies the nano hardness and elasticity modulus of film and substrate using nano-indenter test.It is limited by measurement means
System cannot accurately measure the true mechanical property of film when film thickness is less than 30nm, so the Al of selection 100nm thickness2O3It is thin
Carry out nano-indenter test on film, the hardness and elastic modulus result of testing film and 925 silver medals is as shown in Figure 4.
Since quality is soft, 925 silver surfaces are easily scratched, and scratch surface causes the diffusing reflection of light to will affect its ornamental value.By
Result in Fig. 4 is it is found that ALD Al2O3Hardness with 925 silver medals is respectively 11.45 ± 1.9GPa and 1.78 ± 0.26GPa, difference
6.4 times, illustrate ALD Al2O3Film resists the ability of hard object indentation much higher than 925 silver medals；ALD Al2O3With the elasticity of 925 silver medals
Modulus is respectively 184.48 ± 15.46GPa and 91.81 ± 8.53GPa, differs only by 2 times, illustrates ALD Al2O3Film resistance to deformation
Ability be higher than 925 silver medals, this is because film mainly by Jiang Gao can Al-O key form, it is seen then that 925 silver surfaces deposit ALD
Al2O3Its Marresistance energy can be improved in film.
5、Al2O3The mechanism of action of the film thickness to 925 silver medal comprehensive performance of plated film
According to being measured in experimental example 1-4 as a result, in view of ALD Al2O3It solves 925 silver jeweleries and is asked intolerant to scratching with easy to change
Topic, the present invention deposit the Al of different-thickness using technique for atomic layer deposition in 925 silver surfaces2O3Film, with system thinking plated film
The relationship of the color difference of silver strip, resistance to scratching and discoloration-resisting and film thickness.Take this, proposes film thickness to the color difference of plated film silver strip, scratch-resistant
Wipe the mechanism of action with discoloration-resisting.
Fig. 5 shows film thickness to the influence schematic diagram of 925 silver medal of plated film, wherein (a) shows that color difference influences in Fig. 5, Fig. 5
In (b) be in fastness influence and Fig. 5 (c) be hardness influence.In legend, it can be seen that aluminium oxide, negative sulfidion,
925 silver medals);Diamond penetrator (yellow up-side down triangle), it is seen that light (green pentagon, width means intensity).
Influencing Mechanism is related to the dynamic equilibrium of thickness and performance, and balancing includes two conflicting aspects:
(1) thickness increase may cause color difference increase.In Fig. 5 shown in (a), the visible light across film increases successively with film thickness
It reduces, the brightness of plated film silver is caused to reduce.Film is uneven in the transmissivity of visible region, and compares in 550-760nm
Transmissivity in 380-550nm is much higher, causes the color of aluminum oxide film to tend to light gold, the color of sample is with thickness
Increase can be dimmed.This is consistent with our experimental result (in such as Fig. 2 (a) and (b)).The reduction of intensification and the brightness of color is not
The color difference of plated film silver is caused to increase avoidablely；
(2) thickness increase can promote fastness and Marresistance energy.In Fig. 5 in (b), the color of the vertical axis from bright to dark
Indicate the increase direction of film thickness.Pellumina is deposited on silver strip, since the integrality of 10nm film is poor, incomplete envelope covering
Silver surface be corroded.With the increase of film thickness, the coverage rate of film is greatly improved, and can isolate connecing for corrosive medium
Touching.This is consistent with the result of light micrograph and surrosion in Fig. 3.In Fig. 5 shown in (c), join in identical load
Under several, diamond penetrator is respectively pressed into pellumina and 925 silver medals, the former is much smaller than the latter at depth of cup.This and the result in Fig. 4
Unanimously；The Marresistance of 925 silver medal of plated film with whether plated film is closely related, within the scope of reasonable film thickness, 925 silver medal of plated film
Marresistance can increase with film and be enhanced.
As it can be seen that most thin film thickness is 15nm, complete discoloration-resisting is shown in vulcanized sodium etchant solution.On the contrary,
It was found that maximum film thickness is 24.8nm, because thicker film has unacceptable color difference.Balance the required optical of plated film silver
Matter and corrosion resistance and Marresistance energy, it can be deduced that conclusion, the film thickness of 24.8nm are optimal.
Obviously, the above embodiments are merely examples for clarifying the description, and does not limit the embodiments.It is right
For those of ordinary skill in the art, can also make on the basis of the above description it is other it is various forms of variation or
It changes.There is no necessity and possibility to exhaust all the enbodiments.And it is extended from this it is obvious variation or
It changes still within the protection scope of the invention.
Claims (10)
1. a kind of method for carrying out plated film improvement Silver Jewelry stability based on atomic layer deposition method, which is characterized in that including being based on
Atomic layer deposition method synthesizes ultra-thin Al in Silver Jewelry deposition2O3The step of film, controls the Al2O3The thickness d of film is > 0-
40nm。
2. the method according to claim 1 for carrying out plated film improvement Silver Jewelry stability based on atomic layer deposition method, special
Sign is, controls the Al2O3The thickness d of film is 10-30.5nm.
3. the method according to claim 2 for carrying out plated film improvement Silver Jewelry stability based on atomic layer deposition method, special
Sign is, controls the Al2O3The thickness d of film is 24.8nm.
4. the side according to claim 1-3 for carrying out plated film improvement Silver Jewelry stability based on atomic layer deposition method
Method, which is characterized in that the atomic layer deposition method carries out Al using trimethyl aluminium and water as reaction source2O3The deposition of film synthesizes.
5. the method according to claim 4 for carrying out plated film improvement Silver Jewelry stability based on atomic layer deposition method, special
Sign is that the reaction temperature of the atomic layer deposition method is 200 DEG C.
6. the method according to claim 4 or 5 that plated film improvement Silver Jewelry stability is carried out based on atomic layer deposition method,
It is characterized in that, the atomic layer deposition method specifically comprises the following steps:
(1) reaction chamber is opened, silver jeweleries sample to be deposited is placed on specimen holder, closes reaction chamber, and carry out vacuumizing place
Reason；
(2) heating mode is opened, set temperature is heated to；
(3) setting is following executes parameter: TMA burst length 1s, TMA soaking time 3s, TMA clarification time 70s, H2The O burst length
1s, H2O clarification time 70s, set carrier gas flux 70sccm, 200 DEG C of growth temperature；And it executes program and carries out atomic layer deposition；
(4) after above-mentioned deposition procedure, be vented and take out sample to get.
7. the side according to claim 1-6 for carrying out plated film improvement Silver Jewelry stability based on atomic layer deposition method
Method, which is characterized in that the method also includes cleaning the Silver Jewelry surface using ethyl alcohol and acetone.
8. the method according to claim 7 for carrying out plated film improvement Silver Jewelry stability based on atomic layer deposition method, special
Sign is that the cleaning step carries out under ultrasonic conditions.
9. the method according to claim 7 or 8 that plated film improvement Silver Jewelry stability is carried out based on atomic layer deposition method,
It is characterized in that, further includes the steps that drying up the Silver Jewelry after cleaning with high pure nitrogen.
10. the Silver Jewelry as made from any one of claim 1-9 the method.
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| CN114442213A (en) * | 2022-03-10 | 2022-05-06 | 江苏微导纳米科技股份有限公司 | Optical device, naked-eye 3D display device, and method for improving optical device resistance |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1994202A1 (en) * | 2006-02-02 | 2008-11-26 | Beneq Oy | Protective coating of silver |
| CN103741118A (en) * | 2013-12-25 | 2014-04-23 | 上海纳米技术及应用国家工程研究中心有限公司 | Preparation method of colorful silver product |
| CN107988586A (en) * | 2017-11-29 | 2018-05-04 | 华南理工大学 | The method that atomic layer deposition prepares zinc oxide nano mitron |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1994202A1 (en) * | 2006-02-02 | 2008-11-26 | Beneq Oy | Protective coating of silver |
| CN103741118A (en) * | 2013-12-25 | 2014-04-23 | 上海纳米技术及应用国家工程研究中心有限公司 | Preparation method of colorful silver product |
| CN107988586A (en) * | 2017-11-29 | 2018-05-04 | 华南理工大学 | The method that atomic layer deposition prepares zinc oxide nano mitron |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114442213A (en) * | 2022-03-10 | 2022-05-06 | 江苏微导纳米科技股份有限公司 | Optical device, naked-eye 3D display device, and method for improving optical device resistance |
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