CN113351579B - Method for treating surface of copper-zinc-tin-sulfur-selenium film through plasma cleaning - Google Patents
Method for treating surface of copper-zinc-tin-sulfur-selenium film through plasma cleaning Download PDFInfo
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- CN113351579B CN113351579B CN202110631562.6A CN202110631562A CN113351579B CN 113351579 B CN113351579 B CN 113351579B CN 202110631562 A CN202110631562 A CN 202110631562A CN 113351579 B CN113351579 B CN 113351579B
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- 238000000034 method Methods 0.000 title claims abstract description 60
- 238000004140 cleaning Methods 0.000 title claims abstract description 55
- SEUJAMVVGAETFN-UHFFFAOYSA-N [Cu].[Zn].S=[Sn]=[Se] Chemical compound [Cu].[Zn].S=[Sn]=[Se] SEUJAMVVGAETFN-UHFFFAOYSA-N 0.000 title claims abstract description 28
- 238000004381 surface treatment Methods 0.000 claims abstract description 38
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 8
- 238000012545 processing Methods 0.000 claims description 9
- 238000005406 washing Methods 0.000 claims 1
- 238000012360 testing method Methods 0.000 abstract description 14
- 239000011669 selenium Substances 0.000 abstract description 5
- 239000010949 copper Substances 0.000 abstract description 4
- 230000003746 surface roughness Effects 0.000 abstract description 3
- 229910052711 selenium Inorganic materials 0.000 abstract 1
- 239000010408 film Substances 0.000 description 30
- 239000007789 gas Substances 0.000 description 21
- 239000010409 thin film Substances 0.000 description 16
- WILFBXOGIULNAF-UHFFFAOYSA-N copper sulfanylidenetin zinc Chemical compound [Sn]=S.[Zn].[Cu] WILFBXOGIULNAF-UHFFFAOYSA-N 0.000 description 13
- 239000000243 solution Substances 0.000 description 13
- 230000000694 effects Effects 0.000 description 10
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- 230000009286 beneficial effect Effects 0.000 description 4
- 238000011049 filling Methods 0.000 description 4
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- 229910017987 Cu—Zn—Sn—S—Se Inorganic materials 0.000 description 3
- KTSFMFGEAAANTF-UHFFFAOYSA-N [Cu].[Se].[Se].[In] Chemical compound [Cu].[Se].[Se].[In] KTSFMFGEAAANTF-UHFFFAOYSA-N 0.000 description 3
- 238000001514 detection method Methods 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 230000031700 light absorption Effects 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 239000001763 2-hydroxyethyl(trimethyl)azanium Substances 0.000 description 2
- MARUHZGHZWCEQU-UHFFFAOYSA-N 5-phenyl-2h-tetrazole Chemical compound C1=CC=CC=C1C1=NNN=N1 MARUHZGHZWCEQU-UHFFFAOYSA-N 0.000 description 2
- 235000019743 Choline chloride Nutrition 0.000 description 2
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 2
- 239000004202 carbamide Substances 0.000 description 2
- 125000001309 chloro group Chemical class Cl* 0.000 description 2
- SGMZJAMFUVOLNK-UHFFFAOYSA-M choline chloride Chemical compound [Cl-].C[N+](C)(C)CCO SGMZJAMFUVOLNK-UHFFFAOYSA-M 0.000 description 2
- 229960003178 choline chloride Drugs 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
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- 230000004048 modification Effects 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- HTNDMKDAPWJPEX-UHFFFAOYSA-L 1-ethyl-4-(1-ethylpyridin-1-ium-4-yl)pyridin-1-ium;diperchlorate Chemical compound [O-]Cl(=O)(=O)=O.[O-]Cl(=O)(=O)=O.C1=C[N+](CC)=CC=C1C1=CC=[N+](CC)C=C1 HTNDMKDAPWJPEX-UHFFFAOYSA-L 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 238000001237 Raman spectrum Methods 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- VVTSZOCINPYFDP-UHFFFAOYSA-N [O].[Ar] Chemical compound [O].[Ar] VVTSZOCINPYFDP-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
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- 239000007864 aqueous solution Substances 0.000 description 1
- 238000003486 chemical etching Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 238000000053 physical method Methods 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- IRPLSAGFWHCJIQ-UHFFFAOYSA-N selanylidenecopper Chemical compound [Se]=[Cu] IRPLSAGFWHCJIQ-UHFFFAOYSA-N 0.000 description 1
- SBIBMFFZSBJNJF-UHFFFAOYSA-N selenium;zinc Chemical compound [Se]=[Zn] SBIBMFFZSBJNJF-UHFFFAOYSA-N 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 230000002311 subsequent effect Effects 0.000 description 1
- -1 tetrabutylammonium hexafluorophosphate Chemical compound 0.000 description 1
- 238000004073 vulcanization Methods 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- NDKWCCLKSWNDBG-UHFFFAOYSA-N zinc;dioxido(dioxo)chromium Chemical compound [Zn+2].[O-][Cr]([O-])(=O)=O NDKWCCLKSWNDBG-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B08—CLEANING
- B08B—CLEANING IN GENERAL; PREVENTION OF FOULING IN GENERAL
- B08B7/00—Cleaning by methods not provided for in a single other subclass or a single group in this subclass
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- 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
-
- 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
- H01L31/18—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
-
- 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 discloses a method for passing plasmaCleaning treatment of copper zinc tin sulfur selenium (Cu) 2 ZnSn(S,Se) 4 ) A method of filming a surface, the method comprising: (1) carrying out no-load cleaning on the plasma cleaning chamber before surface treatment; (2) putting a copper-zinc-tin-sulfur-selenium film sample, vacuumizing until the cavity reaches the specified air pressure, and keeping for a certain time; (3) introducing Ar or Ar and O 2 The mixed gas of (2) is kept for a certain time and then the surface cleaning is started at a specified power; (4) and closing the gas path and vacuumizing for a period of time after the surface is cleaned for a designated time, and then obtaining a sample subjected to surface treatment. The method adopts a plasma cleaning mode to remove the high-conductivity phase on the surface of the copper-zinc-tin-sulfur-selenium film, reduces the surface roughness of the sample, does not form a new phase, avoids the influence and residue of the solution on the sample, and is easy to carry out a comparison test under the same condition by a shielding mode and the like.
Description
Technical Field
The invention relates to the field of photovoltaic devices, photocatalysis and photoelectrocatalysis, in particular to a method for processing the surface of a copper-zinc-tin-sulfur-selenium film by plasma cleaning.
Background
The energy problem is a worldwide problem, which is closely related to the social life of people. Solar energy has always occupied an important place in human history, is undoubtedly a clean energy source, and has huge reserves and is almost inexhaustible. According to statistics, the energy of the sun irradiating the earth surface per second can reach 1.757 multiplied by 10 17 Joule, if it can capture and utilize 0.01% of this energy, can meet the global energy demand. But distribution of solar energy over the earth and the likeDispersed and has large regional difference, which is not beneficial to further utilization. Therefore, the collection of scattered solar energy as concentrated clean energy is a necessary path for the development of solar energy. Photochemical conversion, photothermal conversion and photovoltaic conversion are three methods for human use of solar energy. Among them, the photovoltaic conversion technology can convert light energy into electric energy, which has great significance on energy supply and distribution, and thus becomes a main technology for solar energy utilization.
The copper zinc tin sulfur selenium (CZTSSe) solar cell is an ideal thin film solar cell. The CZTS material has a proper band gap (1-1.5 eV) and a high absorption coefficient (10) 4 ～10 5 cm -1 ) And a higher theoretical photoelectric conversion efficiency (-32.2%). The CZTS material has the advantages of high abundance of element components on the earth, low price and good industrial application potential. And the components of the CZTS material are non-toxic and meet the requirement of environmental protection. It is considered as a potential competitor to both Copper Indium Gallium Selenide (CIGS) and cadmium telluride (CdTe) solar cells, which are semiconductor thin film solar cells. However, since the research team of IBM corporation in 2013 used a hydrazine solution method to prepare a copper zinc tin sulfur selenium thin film solar cell device with a photoelectric conversion efficiency of 12.6%, the device efficiency record of the copper zinc tin sulfur selenium thin film solar cell has not been broken for a long time. Until 2019, the device efficiency of the copper zinc tin sulfur selenium thin film solar cell was not broken through to 12.62% by the team of d.h.kim. But this is far from the theoretical ultimate efficiency of S-Q of 33% and is much lagged compared to the 22.6% device efficiency already achieved for CIGS thin film solar cell devices, which is associated with the complexity of the preparation of the quaternary compound. The problem of interface modification is always a field which is concerned by researchers, and as the CdS/CZTSSe interface is an interface where a space charge layer is located, a secondary phase enriched on the surface of the copper-zinc-tin-sulfur-selenium film is removed by a certain surface treatment method, and a complete, compact and flat film surface is obtained, so that a photovoltaic device with higher efficiency is necessary for further impact.
Chinese patent publication No. CN105633199A proposes an electrochemical treatment method for improving the surface properties of a copper-zinc-tin-sulfur thin film: the copper-zinc-tin-sulfur film material is selenized or vulcanized in a constant-temperature tube type annealing furnace, then placed in an electrochemical workstation, firstly placed in absolute ethyl alcohol to be soaked to remove surface particle impurities, and then placed in a mixed solution of 0.001-1M/L ethyl viologen diperchlorate, 0.001-1M/L tetrabutylammonium hexafluorophosphate and an organic solvent to be subjected to electrochemical treatment. The method disclosed by the invention can effectively remove the high-conductivity secondary phase on the surface of the copper-zinc-tin-sulfur film, reduce the roughness of the surface of the film, optimize the interface characteristic of the contact with the window layer, and is environment-friendly and low in cost. But the subsequent effect of the organic solvent on the sample surface is not removed well.
Chinese patent publication No. CN105633205A proposes an electrochemical treatment method for modifying the surface properties of an absorber layer of a copper-zinc-tin-sulfur thin film solar cell: the copper-zinc-tin-sulfur film material is selenized (or vulcanized) in a constant-temperature tube type annealing furnace, then placed in an electrochemical workstation, and directly put into a mixed solution of 0.001-1M/L salt, inorganic acid and deionized water for electrochemical treatment. The method can remove the high-conductivity copper-rich phase on the surface of the copper-zinc-tin-sulfur film, optimize the interface characteristic of the pn junction of the solar cell device, improve the performance output of the cell, and is environment-friendly and low in cost. Although the invention avoids the residue problem of organic solvent, the problem of corrosion of inorganic salt to the sample is difficult to solve.
The chinese patent publication No. CN105633203B proposes a method for anhydrous electrochemical etching of a surface of a copper-zinc-tin-sulfur thin film material: the method comprises the steps of placing a copper-zinc-tin-sulfur film material in a quartz tube furnace for selenization or vulcanization, placing the copper-zinc-tin-sulfur film material in an electrochemical workstation, heating the copper-zinc-tin-sulfur film material in a mixed solution of 0.001-1M/L anhydrous chlorine salt, choline chloride and urea, wherein the mixed solution is formed by mixing the anhydrous chlorine salt, the choline chloride and the urea according to a mass ratio of 1: 0.1-3, performing electrochemical treatment for 1-600 s, and taking out the copper-zinc-tin-sulfur film material. The method can selectively corrode the surface of the copper-zinc-tin-sulfur film, and not only can remove the copper-selenium secondary phase (Cu) on the surface of the copper-zinc-tin-sulfur film x Se), and the phenomenon of unevenness caused by corrosion of chemical etching in aqueous solution on the surface of the absorbing layer is avoided, so that the method is environment-friendly and simple to operate. But is limited by the limitations of the solution method and is difficult if one wants to characterize the surface treatment effect in different areas of the same cell.
Publication No. CN104617186BThe national patent literature proposes a surface treatment method of a zinc-yellow-tin-ore structure thin-film solar cell light absorption layer: the method comprises forming a light absorbing layer (Cu) 1-a Ag a ) 2 (Zn 1-b Cd b )(Sn 1-c Ge c )(S 1- d Se d ) 4 (wherein a, b, c and d are respectively and independently selected from 0-1) soaking in a solution containing metal ions, and then carrying out annealing treatment; the processed zinc yellow tin ore structure thin-film solar cell light absorption layer can well improve the surface defect of the light absorption layer, can effectively improve the open-circuit voltage, the filling factor and the photoelectric conversion efficiency of the solar cell, and the method has the advantages of high raw material utilization rate, environmental friendliness, low cost and large-scale popularization and application in production. This method partially eliminates the effect of the solution on the sample through a post-annealing process, but is also limited by the limitations of the solution method, which is difficult if one wants to characterize the surface treatment effect in different regions of the same cell.
From the above, the surface treatment process of the cu-zn-sn-s-se thin film at present mainly focuses on the solution method, and various methods are needed to reduce or eliminate the influence of the surface treatment solution on the sample. And the solution method has global effect on the surface of the sample, and a contrast area which is not subjected to surface treatment is difficult to form in the same sample by simply shielding a certain part, which brings difficulty for representing the effect of the surface treatment method more strictly.
Disclosure of Invention
Aiming at the defects in the technology, the invention aims to provide a method for processing the surface of a copper-zinc-tin-sulfur-selenium film by plasma cleaning.
The invention provides a method for processing the surface of a copper-zinc-tin-sulfur-selenium film by plasma cleaning, which comprises the following steps:
(1) carrying out no-load cleaning on the plasma cleaning chamber before surface treatment;
(2) putting a copper-zinc-tin-sulfur-selenium film sample, vacuumizing until the cavity reaches the specified air pressure, and keeping for a certain time;
(3) pre-introducing Ar or Ar and O 2 Mixed gas ofAfter a certain time, starting surface cleaning at a specified power;
(4) and closing the gas path and vacuumizing for a period of time after the surface is cleaned for a designated time, and then obtaining a sample subjected to surface treatment.
Preferably, the no-load cleaning gas component in the step (1) is Ar, and the gas flow is 200-500 mL/min.
Preferably, the cleaning power of the idle cleaning in the step (1) is 50-400W.
Preferably, the air pressure in the cavity of the no-load cleaning in the step (1) is 1 × 10 -3 -1×10 0 Torr。
Preferably, the time of the no-load cleaning in the step (1) is 5-60 min.
Preferably, the pressure in the chamber in step (2) is 1 × 10 -3 -1×10 0 Torr。
Preferably, the holding time in step (2) is 1 to 60 min.
Preferably, the total gas flow in step (3) is 200 and 500 mL/min.
Preferably, Ar to O is introduced in the step (3) 2 The volume ratio is 20:1-2: 1.
Preferably, in the step (3), the cleaning power is 50-400W, and the cleaning time is 10-120 s.
Compared with the prior art, the invention at least has the following technical effects:
the method provided by the invention can uniformly clean the surface of the copper zinc tin sulfur selenium film under the condition of less influence on the surface of the copper zinc tin sulfur selenium film, and removes secondary phases enriched on the surface of a sample. The surface of the sample subjected to surface treatment has a perfect macro-crystalline shape, the whole sample is smoother, the surface wettability is improved, and the subsequent processes can be carried out by methods such as spin coating, chemical water bath, hydrothermal method and the like. For photovoltaic devices, the samples were surface treated to improve the CdS/CZTSSe interfacial contact. Compared with a device without surface treatment, the open-circuit voltage and the short-circuit current density of the device after surface treatment are slightly reduced, but the filling factor is improved, and the efficiency of the device is almost unchanged. The higher filling factor is more beneficial to the preparation of future high-performance devices.
Drawings
FIG. 1(a) is a SEM image of the surface of a CuZnSn-S-Se thin film without surface treatment, and FIG. 1(b) is a SEM image of the surface of a CuZnSn-S-Se thin film with surface treatment.
FIG. 2 is a Raman test chart of the Cu-Zn-Sn-S-Se thin film without surface treatment and after surface treatment.
FIG. 3 is a J-V test chart of Cu-Zn-Sn-S-Se thin films without surface treatment and with surface treatment.
Detailed Description
The technical solution of the present invention is further described below with reference to the accompanying drawings and the detailed description.
The invention provides a method for processing the surface of a copper-zinc-tin-sulfur-selenium film by plasma cleaning, which comprises the following steps:
before surface treatment, carrying out no-load cleaning on the plasma cleaning chamber, removing adsorbed substances in the chamber, and eliminating the influence of the previous cleaning;
putting a sample, vacuumizing until the cavity reaches specified air pressure, and keeping for a certain time to remove adsorbed gas on the surface of the sample and in the cavity;
pre-introducing Ar or Ar and O 2 The mixed gas of (2) is kept for a certain time and then the surface cleaning is started at a specified power;
and closing the gas path and vacuumizing for a period of time after the surface is cleaned for a designated time, and then obtaining a sample subjected to surface treatment.
The invention has simple equipment, fewer steps, and stronger surface etching capability and O of Ar plasma 2 The activation capability of the plasma can improve the etching nonuniformity of the single Ar plasma and reduce the damage of the single Ar plasma to the surface of the sample, thereby realizing better etching effect.
The detection means of the surface phase of the sample is Raman spectrum analysis, the detection means of the surface appearance of the sample is a scanning electron microscope, and the detection means of the performance of the sample preparation device is voltage-current density curve test.
From the SEM of fig. 1, it can be seen that the surface of the sample after the surface treatment is perfect and more flat, which indicates that the sample treated by the method has less damage to the surface of the sample and slightly reduces the surface roughness.
The Raman of FIG. 2 shows that the intensity of the Raman peak corresponding to ZnSe is reduced, which indicates that the method has a certain removal effect on the secondary phase on the surface of the sample. The signal intensity of three Raman peaks corresponding to CZTSe and the signal intensity of Raman peaks corresponding to CZTS are improved, which shows that the crystallization quality of the crystal on the surface of the sample is better, and the method removes the part with poor surface crystallization quality.
It can be seen from the J-V test of fig. 3 that the open-circuit voltage and the short-circuit current density of the device treated by the method are slightly reduced, but the fill factor is improved and the device efficiency is almost unchanged, compared with the device without surface treatment. The method is a softer surface treatment method, the influence on the performance of the device after treatment is small, and the higher filling factor is more beneficial to preparing a high-efficiency device.
Compared with other patents, the method has the advantages that the physical method is adopted for surface treatment, the influence of a solution system on a sample in the surface treatment process by the solution method is avoided, and a post-annealing step is not required to be added after the surface treatment. The method can also cause areas with different surface treatment effects on the same sample in a simple shielding mode, is more flexible than a solution method, and is beneficial to more finely regulating and controlling devices.
The following are typical but non-limiting specific embodiments of the present invention:
example 1
A method for processing the surface of a copper-zinc-tin-sulfur-selenium film by plasma cleaning comprises the following steps:
(1) introducing Ar into the plasma cleaning chamber, wherein the gas flow is 300mL/min, and the preparation air pressure is 1 × 10 -2 Torr, the chamber was cleaned with a 250W idle load for 10 min.
(2) Putting the sample into a chamber, and cleaning with Ar and O 2 The volume ratio is 10:1, the total gas flow is 300mL/min, the cleaning power is 150W, and the cleaning time is 30 s.
And closing the gas circuit and vacuumizing for a period of time after the surface is cleaned, taking out the copper-zinc-tin-sulfur-selenium film after the surface treatment, and representing that no new phase is generated on the surface through a Raman test, and representing that macro crystals on the surface are intact and no obvious etching chips exist through an SEM test.
Example 2
A method for processing the surface of a copper-zinc-tin-sulfur-selenium film through plasma cleaning comprises the following steps:
(1) introducing Ar into the plasma cleaning chamber, wherein the gas flow is 200mL/min, and the preparation air pressure is 1 × 10 -3 Torr, the chamber was idle cleaned at 150W for 20 min.
(2) Putting the sample into a chamber, and cleaning with Ar and O 2 The volume ratio is 5:1, the total gas flow is 350mL/min, the cleaning power is 200W, and the cleaning time is 20 s.
And closing the gas path and vacuumizing for a period of time after the surface is cleaned, taking out the copper-zinc-tin-sulfur-selenium film after the surface treatment, and representing that no new phase is generated on the surface through a Raman test, and representing that large crystals on the surface are intact and no obvious etching debris are generated through an SEM test.
Example 3
A method for processing the surface of a copper-zinc-tin-sulfur-selenium film by plasma cleaning comprises the following steps:
(1) introducing Ar into the plasma cleaning chamber, wherein the gas flow is 400mL/min, and the preparation air pressure is 1 × 10 0 Torr, the chamber was idle cleaned at 300W for 5 min.
(2) Putting the sample into a chamber, and cleaning with Ar and O 2 The volume ratio is 2:1, the total gas flow is 400mL/min, the cleaning power is 250W, and the cleaning time is 10 s.
And closing the gas path and vacuumizing for a period of time after the surface is cleaned, taking out the copper-zinc-tin-sulfur-selenium film after the surface treatment, and representing that no new phase is generated on the surface through a Raman test, and representing that large crystals on the surface are intact and no obvious etching debris are generated through an SEM test.
Example 4
A method for processing the surface of a copper-zinc-tin-sulfur-selenium film by plasma cleaning comprises the following steps:
(1) introducing into the plasma cleaning chamberAr, gas flow 400mL/min, preparation pressure 1X 10 0 Torr, the chamber was idle cleaned at 300W for 5 min.
(2) And putting the sample into the chamber, wherein the cleaning gas is Ar, the gas flow is 400mL/min, the cleaning power is 250W, and the cleaning time is 10 s.
Taking out the copper-zinc-tin-sulfur-selenium film after surface treatment, and characterizing that no new phase is generated on the surface through Raman test, but characterizing that a plurality of parts which are not completely etched on the surface of the large crystal are in point distribution through SEM test, which shows that pure Ar etching has poor effect on a sample and can not ensure the uniformity of surface treatment.
From the above all embodiments, it can be known that the high-conductivity phase on the surface of the copper-zinc-tin-sulfur-selenium film can be removed by the argon-oxygen mixed gas plasma cleaning method provided by the invention, the surface roughness of the sample is reduced, no new phase is formed, the influence and residue of the solution on the sample are avoided, the contrast test is easily performed through shielding, and the reliability of the surface treatment experiment is improved.
The above description is only an embodiment of the present invention, but the scope of the present invention is by no means limited thereto, and it should be understood by those skilled in the art that any changes and modifications that can be easily accomplished without departing from the basic principle and the technical scope of the present invention should be considered to be within the scope of the present invention.
Claims (8)
1. A method for processing the surface of a copper-zinc-tin-sulfur-selenium film by plasma cleaning is characterized by comprising the following steps:
(1) before surface treatment, carrying out no-load cleaning on the plasma cleaning chamber, wherein in the step (1), the no-load cleaning gas component is Ar, and the gas flow is 200-500 mL/min;
(2) putting a copper-zinc-tin-sulfur-selenium film sample, vacuumizing until the cavity reaches the specified air pressure, and keeping for a certain time;
(3) pre-introducing Ar and O 2 Maintaining the mixed gas for a certain time, and starting surface cleaning at a specified power, wherein Ar and O are introduced in the step (3) 2 The volume ratio is 20:1-2: 1;
(4) and closing the gas path and vacuumizing for a period of time after the surface is cleaned for a designated time, and then obtaining a sample subjected to surface treatment.
2. The method according to claim 1, wherein the no-load cleaning in step (1) has a cleaning power of 50-400W.
3. The method of claim 1, wherein the chamber pressure in the empty-load cleaning in step (1) is 1 x 10 -3 -1×10 0 Torr。
4. The method according to claim 1, wherein the time of the idle washing in the step (1) is 5-60 min.
5. The method of claim 1, wherein the pressure in the chamber in step (2) is 1 x 10 -3 -1×10 0 Torr。
6. The method according to claim 1, wherein the holding time in step (2) is 1-60 min.
7. The method as claimed in claim 1, wherein the total gas flow in step (3) is 200-500 mL/min.
8. The method according to claim 1, wherein in the step (3), the cleaning power is 50-400W, and the cleaning time is 10-120 s.
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| JPH02194179A (en) * | 1989-01-23 | 1990-07-31 | Ishikawajima Harima Heavy Ind Co Ltd | Film forming device |
| JP3404434B2 (en) * | 1994-09-19 | 2003-05-06 | 株式会社日立製作所 | Cleaning method for microwave plasma device |
| JPH09139349A (en) * | 1995-06-07 | 1997-05-27 | Varian Assoc Inc | Method of cleaning deposit from sputtering cleaning chamber |
| KR20030002465A (en) * | 2001-06-29 | 2003-01-09 | 삼성전자 주식회사 | Method of cleaning chamber plasma |
| CN101214487B (en) * | 2007-01-04 | 2010-09-01 | 北京北方微电子基地设备工艺研究中心有限责任公司 | Method for cleaning cavity of semiconductor etching equipment |
| KR20100115720A (en) * | 2009-04-20 | 2010-10-28 | 주식회사 아이피에스 | Thin film deposition process module for manufacturing solar cell, thin film deposition process system for manufacturing solar cell, and cleaning method for thin film deposition process module |
| CN107755360A (en) * | 2016-08-19 | 2018-03-06 | 合肥欣奕华智能机器有限公司 | A kind of mask plate cleaning device and mask plate purging system |
| CN109671613A (en) * | 2018-11-29 | 2019-04-23 | 贵州振华风光半导体有限公司 | One kind being suitable for substrate circuit nitrogen-hydrogen mixing plasma cleaning method |
| KR102126208B1 (en) * | 2019-04-05 | 2020-06-24 | 김광석 | Plasma apparatus for cleaning foreign substances on photomask surface |
| CN111299253B (en) * | 2020-03-10 | 2022-02-22 | 北京烁科精微电子装备有限公司 | Plasma cleaning device |
| CN111463107B (en) * | 2020-04-07 | 2023-04-28 | 北京晶亦精微科技股份有限公司 | Wafer cleaning equipment |
| CN112609168B (en) * | 2020-11-30 | 2023-06-06 | 中威新能源(成都)有限公司 | Method for rapidly cleaning accumulated film in large-area vacuum chamber |
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