CN107086251A - A kind of method for etching copper-zinc-tin-sulfur film surface second phase - Google Patents
A kind of method for etching copper-zinc-tin-sulfur film surface second phase Download PDFInfo
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- CN107086251A CN107086251A CN201710256059.0A CN201710256059A CN107086251A CN 107086251 A CN107086251 A CN 107086251A CN 201710256059 A CN201710256059 A CN 201710256059A CN 107086251 A CN107086251 A CN 107086251A
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- hydrochloric acid
- tin
- zinc
- copper
- film surface
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- WILFBXOGIULNAF-UHFFFAOYSA-N copper sulfanylidenetin zinc Chemical compound [Sn]=S.[Zn].[Cu] WILFBXOGIULNAF-UHFFFAOYSA-N 0.000 title claims abstract description 38
- 238000005530 etching Methods 0.000 title claims abstract description 31
- 238000000034 method Methods 0.000 title claims abstract description 27
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 142
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000008367 deionised water Substances 0.000 claims abstract description 19
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 19
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000006243 chemical reaction Methods 0.000 claims abstract description 9
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 5
- 239000007788 liquid Substances 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 239000003643 water by type Substances 0.000 claims description 3
- 239000011592 zinc chloride Substances 0.000 claims description 2
- 239000000243 solution Substances 0.000 abstract description 30
- 239000012895 dilution Substances 0.000 abstract description 4
- 238000010790 dilution Methods 0.000 abstract description 4
- 239000002253 acid Substances 0.000 description 14
- 150000003839 salts Chemical class 0.000 description 14
- NNFCIKHAZHQZJG-UHFFFAOYSA-N potassium cyanide Chemical compound [K+].N#[C-] NNFCIKHAZHQZJG-UHFFFAOYSA-N 0.000 description 7
- 238000010586 diagram Methods 0.000 description 6
- 238000001069 Raman spectroscopy Methods 0.000 description 5
- 239000010949 copper Substances 0.000 description 5
- 239000011135 tin Substances 0.000 description 5
- 239000011701 zinc Substances 0.000 description 5
- 238000004073 vulcanization Methods 0.000 description 4
- 230000006378 damage Effects 0.000 description 3
- 239000003814 drug Substances 0.000 description 3
- 231100000614 poison Toxicity 0.000 description 3
- 229910052718 tin Inorganic materials 0.000 description 3
- 208000027418 Wounds and injury Diseases 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 238000000137 annealing Methods 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 229940079593 drug Drugs 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 208000014674 injury Diseases 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 230000007096 poisonous effect Effects 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 1
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 1
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 229910052976 metal sulfide Inorganic materials 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 210000002345 respiratory system Anatomy 0.000 description 1
- 229910052711 selenium Inorganic materials 0.000 description 1
- 239000011669 selenium Substances 0.000 description 1
- 231100000004 severe toxicity Toxicity 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 208000011580 syndromic disease Diseases 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/0248—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies
- H01L31/0256—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies characterised by the material
- H01L31/0264—Inorganic materials
- H01L31/032—Inorganic materials including, apart from doping materials or other impurities, only compounds not provided for in groups H01L31/0272 - H01L31/0312
- H01L31/0326—Inorganic materials including, apart from doping materials or other impurities, only compounds not provided for in groups H01L31/0272 - H01L31/0312 comprising AIBIICIVDVI kesterite compounds, e.g. Cu2ZnSnSe4, Cu2ZnSnS4
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Abstract
The invention provides a kind of method for etching copper-zinc-tin-sulfur film surface second phase.This method makes concentrated hydrochloric acid（Mass fraction is 37.5%）Mixed to be diluted concentrated hydrochloric acid by predetermined volume ratio with deionized water, hydrochloric acid solution after dilution is placed in the water-bath of constant temperature, film sample to be etched is placed in the hydrochloric acid solution after dilution, after making film sample and hydrochloric acid reaction for a period of time, sample is taken out again, finally film surface is rinsed well with deionized water, then dried up with nitrogen gun, then can obtain relatively simple pure phase CZTS films.The present invention soaks copper-zinc-tin-sulfur film using hydrochloric acid solution, can effectively remove bis- dephasigns of ZnS on copper-zinc-tin-sulfur film surface, the preferable CZTS solar cells of photoelectric properties can be subsequently made.The present invention is simple to operation compared to traditional KCN lithographic methods, and cost is low and smaller to the harmfulness of people.
Description
Technical field
The present invention relates to film lithographic technique field, specifically a kind of etching copper-zinc-tin-sulfur film surface second phase
Method.
Background technology
At present, copper-zinc-tin-sulfur（Cu2ZnSnS, writes a Chinese character in simplified form：CZTS）Material less expensive and rich reserves zinc and tin element
Substitute CIGS（CIGS）In indium and gallium, so as to substantially reduce cost, be more suitable for large-scale application.CZTS have with too
The energy gap that solar spectrum matches（1.5 eV）With in visible-range more than 104 cm-1Absorption coefficient, theoretical light
Photoelectric transformation efficiency, more than 30%, is a kind of good absorption layer material.But because CZTS is multi-element compounds, stoichiometry compares
Hardly possible control, the bad just easy generation binary dephasign of stoichiometric proportion control, for example：Cu2S, ZnS etc., are unfavorable for the photo electric of battery
Energy.
In order to remove the dephasign on CZTS surfaces, typically now from potassium cyanide（KCN）Solution performs etching film surface, leads to
The film crossed after KCN etchings can obtain relatively simple pure phase CZTS, improve the efficiency of CZTS solar cells.But it is due to
KCN is a kind of poisonous drugs, and Long Term Contact cyanide occurs that neurasthenic syndrome, eye and the upper respiratory tract are stimulated, to human body
Great bodily injury, and the easy deliquescence of itself are caused, is also a kind of high poison medicine with water reaction generation HCN.
The content of the invention
It is an object of the invention to provide a kind of method for etching copper-zinc-tin-sulfur film surface second phase, this method uses salt
Acid solution etches copper-zinc-tin-sulfur film, simple to operation compared to traditional KCN etchings, and cost is low and smaller to the harmfulness of people.
The object of the present invention is achieved like this：A kind of method for etching copper-zinc-tin-sulfur film surface second phase, including such as
Lower step：
A, the concentrated hydrochloric acid for being 37.5% by mass fraction and deionized water are 0% ~ 5% ratio mixing by volume, hydrochloric acid are made molten
Liquid；
B, copper-zinc-tin-sulfur film to be etched is placed in the hydrochloric acid solution being made in step a；
C, the solution in step b is placed in water-bath, the temperature in water-bath is 70 DEG C ~ 90 DEG C；
D, hydrochloric acid and copper-zinc-tin-sulfur film surface bis- phase reactions of ZnS, generate ZnCl2It is soluble in water；
E, copper-zinc-tin-sulfur film taken out from hydrochloric acid solution, dried up with deionized water rinsing and with nitrogen gun.
It is preferred that, the volume ratio of concentrated hydrochloric acid and deionized water is 1% ~ 3% in step a.It is furthermore preferred that concentrated hydrochloric acid in step a
Volume ratio with deionized water is 1%.
It is preferred that, water-bath is the water-bath of constant temperature in step c.It is furthermore preferred that the temperature in step c in water-bath is 75
℃。
After the bis- phase reaction 1min ~ 10min of ZnS for making hydrochloric acid and copper-zinc-tin-sulfur film surface in step e, then by copper zinc-tin
Sulphur film takes out from hydrochloric acid solution.
In step b, copper-zinc-tin-sulfur film to be etched is placed in the hydrochloric acid solution being made in step a, and hydrochloric acid solution
It is excessive.
To reduce injury of the poisonous drugs to people, the present invention is replaced the KCN of severe toxicity using hydrochloric acid solution, makes concentrated hydrochloric acid（Matter
It is 37.5% to measure fraction）With deionized water by different volumes than being mixed to be diluted to concentrated hydrochloric acid, the hydrochloric acid after dilution is molten
Liquid is placed in the water-bath of constant temperature, and film sample to be etched is placed in the hydrochloric acid solution after dilution, makes film sample and salt
Acid reaction for a period of time after, then sample taken out, finally rinsed well film surface with deionized water, then blown with nitrogen gun
It is dry, then it can obtain relatively simple pure phase CZTS films.
Copper-zinc-tin-sulfur film in the present invention is the film after vulcanization annealing, after hydrochloric acid solution immersion vulcanization annealing
Copper-zinc-tin-sulfur film removes bis- dephasigns of ZnS of film surface, and the preferable CZTS solar cells of photoelectric properties can be subsequently made.
Method in the present invention can also be used to etch copper zinc tin sulfur selenium（CZTSSe）Film, no matter and prepare CZTS films,
Which kind of method is the method for CZTSSe films be.
Brief description of the drawings
Fig. 1 is the Raman spectrograms that salt acid etch CZTS film rear films are used in 1 ~ embodiment of the embodiment of the present invention 3.
Fig. 2 is the enlarged diagram shown in dotted line frame in Fig. 1.
In Fig. 3, a figures are schemed using the SEM of salt acid etch CZTS film rear films in embodiment 3, during b figures are embodiment 1
Schemed using the SEM of salt acid etch CZTS film rear films, c figures are that salt acid etch CZTS film rear films are used in embodiment 2
SEM schemes.
Fig. 4 is the EDS spectrograms of Cu, Zn and Sn in CZTS films after etching in 1 ~ embodiment of the embodiment of the present invention 3.
Fig. 5 is Cu/ (Zn+Sn), the Zn/Sn proportionate relationship schematic diagram drawn according to Fig. 4.
Fig. 6 is the I-V curve schematic diagram of obtained CZTS solar cells in 1 ~ embodiment of the embodiment of the present invention 3.
Fig. 7 is the QE spectrograms of obtained CZTS solar cells in 1 ~ embodiment of the embodiment of the present invention 3.
Fig. 8 is the Raman that salt acid etch CZTS film rear films are used in the embodiment of the present invention 1,4 ~ embodiment of embodiment 7
Spectrogram.
Fig. 9 is the enlarged diagram shown in dotted line frame in Fig. 8.
Embodiment
The present invention can be reacted based on hydrochloric acid with metal sulfide, and hydrochloric acid solution is soaked into copper-zinc-tin-sulfur film, be invented
A kind of method of new etching CZTS film surface secondary phases.Wherein hydrochloric acid solution is to use concentrated hydrochloric acid（Mass fraction is 37.5%）
It is formulated from deionized water with different volume ratios, additionally needs water-bath and certain temperature is provided, so as to promotes anti-
The completion answered, the different reaction time are also different to the etching effect of film, can look for the optimal reaction time from
And obtain best etching effect.The method of etching CZTS film surfaces provided by the present invention is simple to operation, and human body is endangered
Evil property is smaller, and can be good at etching the secondary dephasign of film surface.The present invention is described in detail with specific embodiment below.
Embodiment 1
The method that copper-zinc-tin-sulfur film surface second phase is etched in the present embodiment comprises the following steps：
A, the concentrated hydrochloric acid for being 37.5% by mass fraction and deionized water are 1% ratio mixing by volume, and hydrochloric acid solution is made.
B, the copper-zinc-tin-sulfur film after vulcanization to be etched is placed in the hydrochloric acid solution being made in step a, and ensures salt
Acid solution is excessive.
C, the solution in step b is placed in the water-bath of a constant temperature, the temperature setting of water-bath is 75 DEG C.
D, hydrochloric acid and copper-zinc-tin-sulfur film surface bis- dephasigns of ZnS react, and reaction equation is：
React the ZnCl of generation2It is soluble in water, thus successfully eliminate bis- dephasigns of ZnS of CZTS film surfaces.
E, make in step d after hydrochloric acid and ZnS reaction 5min, copper-zinc-tin-sulfur film to be taken out from hydrochloric acid solution, spend from
Sub- water is rinsed well, then is dried up with nitrogen gun.
It is to complete the process performed etching to the secondary phase on copper-zinc-tin-sulfur film surface by five steps of a ~ e above,
CZTS films after etching are grown into CdS cushions, sputtering ZnO and ITO Window layers by CBD methods, top electrode Al is evaporated, then
Final CZTS solar cells are arrived.
Embodiment 2
Compared with Example 1, mass fraction is pressed into body for 37.5% concentrated hydrochloric acid and deionized water in step a in the present embodiment
Hydrochloric acid solution is made than being mixed for 3% ratio in product；The step of other in the present embodiment is same as Example 1.
Embodiment 3
Compared with Example 1, mass fraction is pressed into body for 37.5% concentrated hydrochloric acid and deionized water in step a in the present embodiment
Product for 0% ratio than mixing, and the hydrochloric acid solution being made in hydrochloric acid solution, i.e. the present embodiment is that the hydrochloric acid that mass fraction is 0% is molten
Liquid, namely all deionized waters of hydrochloric acid solution；The step of other in the present embodiment is same as Example 1.Precisely, this reality
It is the example that unused hydrochloric acid etches copper-zinc-tin-sulfur film in fact to apply example.
CZTS films after to being etched in 1 ~ embodiment of embodiment 3 carry out Raman scattering tests, are used during test
325nm laser, acquired results are shown in Fig. 1 and Fig. 2, and Fig. 2 is the enlarged drawing shown in dotted line frame in Fig. 1.Can be with by Fig. 1 and Fig. 2
Find out, the peak intensity with the increase ZnS of concentration of hydrochloric acid substantially weakens, CZTS peak intensity is relative to be strengthened, this explanation hydrochloric acid can be gone
Except the ZnS of film surface, and concentration of hydrochloric acid is bigger, and the ZnS of etching ability is bigger.
CZTS films after to being etched in 1 ~ embodiment of embodiment 3 are scanned Electronic Speculum test, and acquired results are shown in Fig. 3,
In Fig. 3, a figure correspondence embodiments 3, b figure correspondence embodiments 1, c figure correspondence embodiments 2.As seen from Figure 3, with hydrochloric acid solution
The secondary phase ZnS of the increase film surface of concentration is fewer and fewer.
CZTS films after to being etched in 1 ~ embodiment of embodiment 3 carry out power spectrum test, and acquired results are shown in Fig. 4 and Fig. 5.
As can be seen from Figure 4 and Figure 5, with the increase of concentration of hydrochloric acid solution, Zn content is reducing in etching rear film, Cu and Sn's
Relative amount is increased slightly, and these prove that salt acid soak can effectively remove the ZnS secondary phases of film surface.
I-V tests are carried out to CZTS solar cells obtained in 1 ~ embodiment of embodiment 3, acquired results are shown in Fig. 6.By scheming
6 understand, for the CZTS solar cells of unused salt acid etch CZTS films（Curve shown in square frame 0% in corresponding diagram）, its short circuit electricity
Current density is Jsc=12.98 mA/cm2, its open-circuit voltage is Voc=390V, its fill factor, curve factor is FF=42.42%, and battery efficiency is about
For Eff.=2.15%.Etched by volume for 1% hydrochloric acid solution being configured to after CZTS films with concentrated hydrochloric acid and deionized water, institute
The CZTS solar cells being made（Curve shown in circle 1% in corresponding diagram）, its short-circuit current density is Jsc=13.37 mA/cm2, its
Open-circuit voltage is Voc=656 V, its fill factor, curve factor be FF=53.9%, battery efficiency is about Eff.=4.73%, it is seen then that battery it is short
Road current density, Jsc, open-circuit voltage Voc, fill factor, curve factor FF and battery efficiency Eff. be obviously improved than having of not etching,
Battery efficiency is twice before unused salt acid etch.But when the concentration of increase hydrochloric acid makes concentrated hydrochloric acid and deionized water by volume 3%
After preparation, etch CZTS films and CZTS solar cells are made（See curve shown in Fig. 6 intermediate cams shape 3%）, its short-circuit current density
For Jsc=10.67 mA/cm2, its open-circuit voltage is Voc=331 V, its fill factor, curve factor is FF=39.94%, and battery efficiency is about Eff.
=1.41%, it is clear that the short-circuit current density J of batterysc, open-circuit voltage Voc, fill factor, curve factor FF and battery efficiency Eff. be than unused
Salt acid etch have dropped.Although reason, which is too high concentration of hydrochloric acid, can etch more ZnS, absorbed layer CZTS is caused
Destruction, have impact on the ability of its carrier transport, therefore, it is necessary to choose conjunction when with the secondary phases of salt acid etch CZTS film surfaces
Suitable concentration.
Quantum efficiency test is carried out to CZTS solar cells obtained in 1 ~ embodiment of embodiment 3, acquired results are shown in figure
7.As seen from Figure 7, etched by volume for 1% hydrochloric acid solution being configured to after CZTS films with concentrated hydrochloric acid and deionized water,
The quantum efficiency of made CZTS solar cells is above two other in 400nm-700nm wave bands, thus its integration current compared with
Height, this is corresponding with the electric current in the I-V curve measured.
Embodiment 4
Compared with Example 1, hydrochloric acid reacts 0min with ZnS in the present embodiment, and other are same as Example 1.
Embodiment 5
Compared with Example 1, hydrochloric acid reacts 1min with ZnS in the present embodiment, and other are same as Example 1.
Embodiment 6
Compared with Example 1, hydrochloric acid reacts 3min with ZnS in the present embodiment, and other are same as Example 1.
Embodiment 7
Compared with Example 1, hydrochloric acid reacts 10min with ZnS in the present embodiment, and other are same as Example 1.
CZTS films after being etched to embodiment 1,4 ~ embodiment of embodiment 7 carry out Raman scattering tests, acquired results
See Fig. 8 and Fig. 9, Fig. 9 is the enlarged drawing shown in dotted line frame in Fig. 8.During test, etch 0min CZTS films, using 532nm and
The laser of two different wave lengths of 325nm is irradiated respectively, and ZnS peaks are not found during 532nm wavelength illuminations.Etching 1min,
3min, 5min and 10min CZTS films, are irradiated using the laser of 325nm wavelength.As seen from Figure 8, with
The growth of hydrochloric acid etch period, ZnS feature peak intensity is gradually reduced therewith, illustrates the longer etching film table of hydrochloric acid etch period
Face ZnS ability is stronger.By enlarged drawing in Fig. 9, positioned at 336 cm-1The CZTS at place Characteristic Raman peak, from unused salt
During acid etch, a simply shoulder peak, with the increase of etch period, the intensity at its peak is in relative enhancing.
The embodiment of the present invention etches the CZTS films after vulcanization using hydrochloric acid solution, compared to traditional KCN etchings simply
Easy to operate, cost is relatively low and smaller to the harmfulness of people, and the film after this method etching is compared to CZTS sun electricity that is purer, being made
Pond efficiency substantially has been improved, and this will realize that the CZTSSe batteries of efficient pure phase provide a kind of method of feasibility for future.
Claims (7)
1. a kind of method for etching copper-zinc-tin-sulfur film surface second phase, it is characterized in that, comprise the following steps：
A, the concentrated hydrochloric acid for being 37.5% by mass fraction and deionized water are 0% ~ 5% ratio mixing by volume, hydrochloric acid are made molten
Liquid；
B, copper-zinc-tin-sulfur film to be etched is placed in the hydrochloric acid solution being made in step a；
C, the solution in step b is placed in water-bath, the temperature in water-bath is 70 DEG C ~ 90 DEG C；
D, hydrochloric acid and copper-zinc-tin-sulfur film surface bis- phase reactions of ZnS, generate ZnCl2It is soluble in water；
E, copper-zinc-tin-sulfur film taken out from hydrochloric acid solution, dried up with deionized water rinsing and with nitrogen gun.
2. the method for etching copper-zinc-tin-sulfur film surface second phase according to claim 1, it is characterized in that, it is dense in step a
The volume ratio of hydrochloric acid and deionized water is 1% ~ 3%.
3. the method for etching copper-zinc-tin-sulfur film surface second phase according to claim 2, it is characterized in that, it is dense in step a
The volume ratio of hydrochloric acid and deionized water is 1%.
4. the method for etching copper-zinc-tin-sulfur film surface second phase according to claim 1, it is characterized in that, step c reclaimed waters
Bath is the water-bath of constant temperature.
5. the method for etching copper-zinc-tin-sulfur film surface second phase according to claim 4, it is characterized in that, step c reclaimed waters
Temperature in bath is 75 DEG C.
6. the method for etching copper-zinc-tin-sulfur film surface second phase according to claim 1, it is characterized in that, make in step e
After bis- phase reaction 1min ~ 10min of ZnS on hydrochloric acid and copper-zinc-tin-sulfur film surface, then by copper-zinc-tin-sulfur film from hydrochloric acid solution
It is middle to take out.
7. the method for etching copper-zinc-tin-sulfur film surface second phase according to claim 1, it is characterized in that, will in step b
Copper-zinc-tin-sulfur film to be etched is placed in the hydrochloric acid solution being made in step a, and hydrochloric acid solution is excessive.
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| US20120061790A1 (en) * | 2010-09-09 | 2012-03-15 | International Business Machines Corporation | Structure and Method of Fabricating a CZTS Photovoltaic Device by Electrodeposition |
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Non-Patent Citations (1)
| Title |
|---|
| ANDREW FAIRBROTHER等: ""Development of a Selective Chemical Etch To Improve the Conversion Efficiency of Zn-Rich Cu2ZnSnS4 Solar Cells"", 《J. AM. CHEM. SOC.》 * |
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