CN105088161B - Based on processing method and system that microwave plasma is modified to CIGS surface - Google Patents
Based on processing method and system that microwave plasma is modified to CIGS surface Download PDFInfo
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- CN105088161B CN105088161B CN201510546784.2A CN201510546784A CN105088161B CN 105088161 B CN105088161 B CN 105088161B CN 201510546784 A CN201510546784 A CN 201510546784A CN 105088161 B CN105088161 B CN 105088161B
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Abstract
The invention discloses processing method and system that Yi is always modified based on microwave plasma to CIGS surface.The present invention produces microwave plasma by ionized inert gas, and it is applied to the surface of CIGS CIGS thin film, reverse sputtering and the annealing of high intensity are carried out in micron dimension, the Cu Se phases on surface can not only be removed, film can also further be annealed, weaken the uneven situation of Ga, so as to reach the purpose of material surface modifying；Main absorbed layer of the CIGS thin film as CIGS solar cells, the quality of the layer film directly determines the quality of CIGS solar cells, the CIGS thin film being modified by ECR is that the CIGS batteries for obtaining more high-photoelectric transformation efficiency are laid a good foundation, and by verification experimental verification, it is practical.
Description
Technical field
The present invention relates to solar cell preparation field, and in particular to one kind is based on microwave plasma to CIGS table
Face modified processing method and system.
Background technology
In CIGS CIGS cell manufacturing process, core is also the technique i.e. CIGS preformed layer of most critical the most
Selenized annealing technique.Why crucial this step process is, mainly after annealing process, in the CIGS thin-film as main absorbed layer
The composition on portion and surface is substantially stationary, and easily formation surface has copper Cu- selenium Se phases so that reaction not enough completely, occurs
Impurity energy level, influences the efficiency of battery；Also, it is high near Mo back electrode contents along depth direction gallium Ga contents, near surface element
The feature for dividing content low, causes the band gap of bottom greatly, and the band gap at top is small, causes surface to have shielding to the solar energy of component frequency
Effect.Traditional mode is that surface is processed with KCN and other compounds for containing CN-, removes the Cu-Se phases on surface
Or weakening Ga distribution gradients in the depth direction by improving annealing temperature, this method is a kind of non-from scientific research
Normal effective method, but due to the toxicity of cyanide itself in industrialization process, generation that can for no reason is many negative
Influence：Such as environmental assessment, cyanide are taken precautions against.
The content of the invention
Surface for CIGS thin film present in currently available technology is easily formed Cu-Se and Ga contents along depth point
The uneven problem of cloth, microwave electron cyclotron resonance (ElectronCyclotron is based on the invention provides one kind
Resonance, ECR) plasma (this plasma abbreviation microwave plasma, it is also possible to referred to as ecr plasma) is to copper
Indium gallium selenium surface modified processing method and system, by the present invention, can not only remove the Cu-Se phases on surface, can also be right
CIGS thin film is further annealed, and weakens the uneven situation of Ga.
It is an object of the present invention to provide a kind of place modified to the surface of CIGS based on microwave plasma
Reason system.
The processing system modified to the surface of CIGS based on microwave plasma of the invention includes：Microwave power
Source, Transmission system, waveguide turn coaxial, microwave plasma generating chamber, microwave plasma produce field coil, deflection coil,
Specimen holder and vacuum chamber；Wherein, microwave power source sends microwave；Microwave is transmitted to waveguide by Transmission system and turns coaxial；Ripple
Lead and turn coaxial by microwave feed-in microwave plasma generating chamber；Microwave plasma produces outdoor to be wound with microwave plasma product
Magnetisation field coil, produces the magnetic field matched with the frequency of microwave, microwave by the ionized inert gas in plasma generation chamber,
Produce microwave plasma；Microwave plasma generating chamber is connected with vacuum chamber；Specimen holder is provided with vacuum chamber, is prepared
On the specimen holder that CIGS thin film is placed in vacuum chamber；Deflection coil includes two coils, and a coil is wrapped in the outer of vacuum chamber
Wall, another coil is wrapped in around specimen holder, and the magnetic field that deflection coil is produced is by microwave plasma from microwave plasma
Body generating chamber leads to specimen holder；High pressure is loaded between microwave plasma generating chamber and specimen holder, enhancing CIGS thin film
Surface treatment effect.
Being wrapped in microwave plasma produces outdoor microwave plasma to produce field coil, the magnetic field intensity B of generation
Frequency f with microwave matches, and meets the π f=eB/m of relation 2e, wherein, e is 1.6*10^-9 coulombs of unit electron charge, meFor
Per-unit electronics quality 9.1*10^-31kg.
High pressure is loaded between microwave plasma generating chamber and specimen holder, in test, setting high pressure is with stability microwave
Plasma and do not destroy premised on sample surfaces, grope through overtesting, voltage should be between 200V~1000V, to strengthen
The beam intensity of microwave plasma.
It is another object of the present invention to provide a kind of modified to the surface of CIGS based on microwave plasma
Processing method.
The processing method modified to the surface of CIGS based on microwave plasma of the invention, comprises the following steps：
1) molybdenum Mo films are prepared on substrate by sputtering method；
2) CIGS thin film is prepared on Mo films by sputtering and selenization technique method or three stage Co-evaporation method；
3) on the specimen holder that the CIGS thin film that will be prepared is placed in vacuum chamber；
4) power supply that microwave plasma produces field coil is opened, regulation electric current makes microwave plasma produce magnetic field line
Enclose the magnetic field for producing to match with the frequency of microwave, magnetic field basis is provided for microwave plasma is produced；
5) inert gas is sent into microwave plasma generating chamber；
6) microwave power source is opened, the frequency f of microwave is adjusted, basis is provided for microwave plasma is produced, now microwave
The ionized inert gas of plasma generation chamber, produce microwave plasma；
7) power supply of deflection coil is opened, microwave plasma is produced in the magnetic field that deflection coil is produced from microwave plasma
Raw room leads to specimen holder, and CIGS thin film is processed；
8) high voltage power supply is opened, high pressure is loaded between microwave plasma generating chamber and specimen holder and is strengthened plasma beam
Intensity of flow, strengthens the surface treatment effect of CIGS thin film；
9) high voltage power supply, microwave power source, magnetic field power supply are closed after having processed successively, and CIGS thin film is taken out, copper and indium
The surface modification treatment of gallium selenium is completed.
Wherein, in step 1) in, substrate uses glass substrate or flexible substrate, and flexible substrate is using titanium, stainless
Steel or polyimides.
In step 4) in, microwave plasma produces the frequency f phases of the magnetic field intensity B that field coil is produced and microwave
Match somebody with somebody, meet the π f=eB/m of relation 2e, wherein, e is 1.6*10^-9 coulombs of unit electron charge, meIt is unit electron mass 9.1*10
^-31kg。
In step 7) in, treatment is carried out to CIGS thin film includes three kinds of processes：
A) microwave plasma reverse sputtering effect, removes the Cu-Se phases on CIGS thin film surface, so as to realize that surface is modified；
B) selenium of free state absorbs the electronics in microwave plasma, becomes divalence selenium, contributes to the lifting of battery efficiency,
Equation is as follows：
Se0+ 2e=Se2-；
C) surface of CIGS thin film is acted on due to microwave plasma so that CIGS thin film heats up, and further functions as and moves back
The effect of fire, so that it is uniform along depth direction Ga content distributions, and crystal grain becomes big.
In step 8) in, be carried in the high pressure between microwave plasma generating chamber and specimen holder, voltage 200V~
Between 1000V.
In step 9) in, magnetic field power supply refers to the electricity of power supply and microwave plasma the generation field coil of deflection coil
Source.
Complete CIGS surface modification treatment after, the surface of CIGS thin-film be sequentially prepared cadmium sulfide CdS,
Zinc oxide ZnO and zinc oxide aluminum AZO films, prepare copper indium gallium selenium solar cell.
Microwave plasma is the plasma based on electron cyclotron resonace, with high electron density, low electron energy, height
The characteristics such as degree of ionization.Using these characteristics, by ionized inert gas, and CIGS surfaces are applied to, height is carried out in micron dimension
The reverse sputtering of intensity and annealing, so as to reach the purpose of material surface modifying.Main absorptions of the CIGS as CIGS solar cells
Layer, the quality of the layer film directly determines the quality of CIGS solar cells, and the CIGS being modified by ECR is acquisition more bloom
The CIGS of photoelectric transformation efficiency lays a good foundation, and by verification experimental verification, it is practical.
Advantages of the present invention：
The present invention produces microwave plasma by ionized inert gas, and is applied to the surface of CIGS thin film,
Reverse sputtering and the annealing of high intensity are carried out in micron dimension, the Cu-Se phases on surface can be not only removed, film can also be carried out
Further annealing, weakens the uneven situation of Ga, so as to reach the purpose of material surface modifying；CIGS thin film as CIGS too
The main absorbed layer of positive energy battery, the quality of the layer film directly determines the quality of CIGS solar cells, is modified by ECR
CIGS thin film is that the CIGS batteries for obtaining more high-photoelectric transformation efficiency are laid a good foundation, and by verification experimental verification, it is practical.
Brief description of the drawings
Fig. 1 is the structural representation of the processing system modified to the surface of CIGS based on microwave plasma of the invention
Figure；
Fig. 2 is the flow chart of the processing method modified to the surface of CIGS based on microwave plasma of the invention.
Specific embodiment
Below in conjunction with the accompanying drawings, by embodiment, the present invention will be further described.
As shown in figure 1, the modified processing system in the surface to CIGS of the present embodiment includes：Microwave power source 1, biography
Defeated system 2, waveguide turns coaxial 3, microwave plasma generating chamber 4, microwave plasma and produces field coil 5, deflection coil, sample
Product frame 7 and vacuum chamber 8；Wherein, microwave power source 1 sends microwave；Microwave is transmitted to waveguide by Transmission system 2 and turns coaxial 3；
Waveguide turns coaxial 3 by microwave feed-in microwave plasma generating chamber 4；Be wound with outside microwave plasma generating chamber 4 microwave etc. from
Daughter produces field coil 5；Microwave plasma generating chamber 4 is connected with vacuum chamber 8；Specimen holder 7 is provided with vacuum chamber 8, is made
The CIGS thin film got ready is placed on specimen holder；Deflection coil includes two coils 61 and 62, and a coil 61 is wrapped in vacuum chamber
Outer wall, another coil 62 is wrapped in around specimen holder 7, and the magnetic field that deflection coil is produced is by microwave plasma from microwave
Plasma generation chamber 4 leads to specimen holder 7；High pressure is loaded between microwave plasma generating chamber 4 and specimen holder 7, is strengthened
The surface treatment effect of CIGS thin film.
The modified processing method in the surface to CIGS of the present embodiment, as shown in Fig. 2 comprising the following steps：
1) molybdenum Mo films are prepared on a glass substrate by sputtering method；
2) CIGS thin film is prepared on Mo films by sputtering and selenization technique method or three stage Co-evaporation method；
3) on the specimen holder 7 that the CIGS thin film that will be prepared is placed in vacuum chamber 8；
4) power supply that microwave plasma produces field coil 5 is opened, regulation electric current makes microwave plasma produce magnetic field
The magnetic field B that coil is produced is near 875 Gausses, magnetic field basis to be provided for microwave plasma is produced；
5) argon gas is sent into microwave plasma generating chamber 4；
6) microwave power source 1 is opened, regulation microwave frequency f is 2.45GHz, and basis is provided for microwave plasma is produced,
Now the argon gas ionization of microwave plasma generating chamber, produces microwave plasma；
7) open the power supply of deflection coil, deflection coil produce by microwave plasma from microwave plasma generating chamber
Specimen holder is led to, CIGS thin film is processed；
8) high voltage power supply is opened, on-load voltage is now surveyed to 300V between microwave plasma generating chamber and specimen holder
It is 3A (result of assay optimization) left and right that the beam intensity on CIGS surfaces must be applied to, and strengthens the surface treatment effect of CIGS thin film
Really；
9) high voltage power supply, microwave power supply, magnetic field power supply are closed after having processed successively, and CIGS thin film is taken out, in its table
Face is sequentially prepared cadmium sulfide CdS, zinc oxide ZnO and zinc oxide aluminum AZO films.
It is finally noted that, the purpose for publicizing and implementing mode is that help further understands the present invention, but ability
The technical staff in domain is appreciated that：Without departing from the spirit and scope of the invention and the appended claims, it is various replacement and
Modification is all possible.Therefore, the present invention should not be limited to embodiment disclosure of that, the scope of protection of present invention with
The scope that claims are defined is defined.
Claims (6)
1. the processing method that a kind of surface to CIGS is modified, it is characterised in that the treating method comprises following steps：
1) molybdenum Mo films are prepared on substrate by sputtering method；
2) CIGS CIGS thin film is prepared on Mo films by sputtering and selenization technique method or three stage Co-evaporation method；
3) on the specimen holder that the CIGS thin film that will be prepared is placed in vacuum chamber；
4) power supply that microwave plasma produces field coil is opened, regulation electric current makes microwave plasma produce field coil to produce
Raw magnetic field matches with the frequency of microwave, and magnetic field basis is provided for microwave plasma is produced；
5) inert gas is sent into microwave plasma generating chamber；
6) open microwave power source, adjust microwave frequency f, for microwave plasma produce basis is provided, now microwave etc. from
The ionized inert gas of daughter generating chamber, produce microwave plasma；
7) power supply of deflection coil is opened, the magnetic field that deflection coil is produced is by microwave plasma from microwave plasma generating chamber
Specimen holder is led to, CIGS thin film is processed；
8) high voltage power supply is opened, high pressure reinforcement plasma line is loaded between microwave plasma generating chamber and specimen holder strong
Degree；
9) high voltage power supply, microwave power source, magnetic field power supply are closed after having processed successively, and CIGS thin film is taken out, CIGS
Surface modification treatment complete.
2. processing method as claimed in claim 1, it is characterised in that in step 1) in, substrate uses glass substrate or soft
Property substrate, flexible substrate use titanium, stainless steel or polyimides.
3. processing method as claimed in claim 1, it is characterised in that in step 4) in, microwave plasma produces magnetic field line
Enclose the magnetic field intensity B and frequency f of microwave for producing to match, meet the π f=eB/m of relation 2e, wherein, e is unit electron charge
1.6×10-9Coulomb, meIt is unit electron mass 9.1 × 10-31kg。
4. processing method as claimed in claim 1, it is characterised in that in step 7) in, carrying out treatment to CIGS thin film includes
Three kinds of processes：
A) microwave plasma reverse sputtering effect, removes the Cu-Se phases on CIGS thin film surface；
B) selenium of free state absorbs the electronics in microwave plasma, becomes divalence selenium, and equation is as follows：
Se0+ 2e=Se2-；
C) surface of CIGS thin film is acted on due to microwave plasma so that CIGS thin film heats up.
5. processing method as claimed in claim 1, it is characterised in that be carried in microwave plasma generating chamber and specimen holder it
Between high pressure, voltage is between 200V~1000V.
6. processing method as claimed in claim 1, it is characterised in that after the surface modification treatment for completing CIGS,
The surface of CIGS thin-film is sequentially prepared cadmium sulfide CdS, zinc oxide ZnO and zinc oxide aluminum AZO films, prepares copper and indium gallium
Se solar cell.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106229383B (en) * | 2016-09-10 | 2018-12-11 | 华南理工大学 | A kind of equally distributed copper-indium-galliun-selenium film solar cell of gallium element and preparation method thereof |
| CN106431407B (en) * | 2016-09-23 | 2019-04-12 | 电子科技大学 | A method of two selenizing platinum of sheet is prepared using superhigh-pressure high-temp |
| CN106876507A (en) * | 2017-01-11 | 2017-06-20 | 深圳大学 | Modified Cu base films in a kind of surface and preparation method thereof |
| CN109888278B (en) * | 2017-05-25 | 2021-07-16 | 宁波工程学院 | Electromagnetic field confined plasma enhanced oxidation roasting device for synthesizing high-nickel anode material of lithium ion battery |
| CN109735805A (en) * | 2019-02-21 | 2019-05-10 | 苏州领锐源奕光电科技有限公司 | A kind of preparation method of the indium and tin oxide film of surface plasma influx and translocation |
| CN115498068A (en) * | 2022-09-22 | 2022-12-20 | 深圳先进技术研究院 | CIGS solar cell surface modification method and device and CIGS solar cell |
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| JP2013108116A (en) * | 2011-11-18 | 2013-06-06 | Tokai Rubber Ind Ltd | Plasma modification and film formation apparatus |
| CN103926260A (en) * | 2014-03-31 | 2014-07-16 | 北京工业大学 | ECR-PECVD (electron cyclotron resonance-plasma enhanced chemical vapor deposition) device for ion irradiation experiment |
| CN104134708A (en) * | 2014-08-13 | 2014-11-05 | 北京大学 | Method for ohmic contact between copper indium gallium diselenide and molybdenum and solar cell preparation method |
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Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1317924A (en) * | 2000-12-26 | 2001-10-17 | 北京航空工艺研究所 | Microwave plasma source |
| CN1390977A (en) * | 2002-07-20 | 2003-01-15 | 复旦大学 | Process for preparing compound film at ordinary temp |
| CN102154622A (en) * | 2010-12-06 | 2011-08-17 | 电子科技大学 | Method for preparing copper-indium-gallium-selenium thin film serving as light absorbing layer of solar cell |
| JP2013108116A (en) * | 2011-11-18 | 2013-06-06 | Tokai Rubber Ind Ltd | Plasma modification and film formation apparatus |
| CN103926260A (en) * | 2014-03-31 | 2014-07-16 | 北京工业大学 | ECR-PECVD (electron cyclotron resonance-plasma enhanced chemical vapor deposition) device for ion irradiation experiment |
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