CN103866360A - Method for coplating copper indium gallium selenium prefabricated layer by using ionic liquid through complex waveform pulse - Google Patents
Method for coplating copper indium gallium selenium prefabricated layer by using ionic liquid through complex waveform pulse Download PDFInfo
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Abstract
The invention belongs to the technical field of solar cells, and concretely relates to a method for coplating a copper indium gallium selenium prefabricated layer by using an ionic liquid through complex waveform pulse. The method for coplating the copper indium gallium selenium prefabricated layer by using the ionic liquid through complex waveform pulse is characterized in that the copper indium gallium selenium prefabricated layer is obtained through electrodepositing on a cathode substrate in an electrodepositing solution through current control pulse or voltage control pulse, the current control pulse or voltage control pulse is complex waveform pulse, and the complex waveform pulse comprises a forward pulse period with a negative current and a negative voltage on a deposition surface, a backward pulse period with a positive current and a positive voltage on the deposition surface, and a pause period; and the electrodepositing solution is an ionic liquid system. The above complex waveform pulse technology is used in the electrodepositing process to form the copper indium gallium selenium prefabricated layer and stripping parts of selenium to the above plating solution, so the generation of selenium balls is avoided, thereby the formed copper indium gallium selenium prefabricated layer has uniform components and a stable phase.
Description
Technical field
The invention belongs to area of solar cell, specifically, relate to a kind of method that complicated wave form pulse ion liquid plates copper-indium-galliun-selenium preformed layer altogether.
Background technology
Along with the continuous increase of mankind's energy consumption, the non-renewable energy as exhausting of fossil oil be problem demanding prompt solution.To there is flex point in about the year two thousand thirty in fossil energy total amount consumed, the proportion of renewable energy source will constantly rise, and wherein, the proportion of sun power in future source of energy structure is by increasing, and this proportion of conservative estimation can exceed 60% in 2100.Sun power is the energy the abundantest in numerous renewable energy sources, and the global sunlight energy of a hour is just equivalent to the earth energy consumption of a year, far away higher than wind energy, underground heat, water power, sea energy, bioenergy equal energy source.
The bottleneck of the extensive generating of restriction sun power is mainly low transformation efficiency and the high production cost of photovoltaic device, wherein most crucial key element is the cost of photovoltaic generating system, comprises that photovoltaic panel and other system component are as invertor, electric switch device, cable and support etc.Generating will realize " par online ", and cost of electricity-generating will reach 0.6 yuan of every degree Renminbi, and photovoltaic panel cost will be down to 3 ~ 4 yuan of every watt of Renminbi, 5 ~ 7 yuan of every watt of Renminbi of price.Because existing market polysilicon photovoltaic panel price has approached the cost price of enterprise, polysilicon photovoltaic panel manufacturing technology is also relatively ripe, lowers limited space, realizes " par online " and is not easy with polysilicon photovoltaic panel.
Copper-indium-galliun-selenium (CuIn
xga
yse
z, also can comprise sulphur, being abbreviated as CIGS) and the advantage such as thin film photovoltaic panel is high with its efficiency of conversion, permanent stability good, capability of resistance to radiation is strong becomes the study hotspot of photovoltaic circle, is expected to become follow-on cheap photovoltaic panel.It has following advantage:
1) high photoelectric transformation efficiency, glass substrate CIGS thin film photovoltaic panel laboratory efficiency has exceeded 20% at present, approaches the world record of traditional crystal silicon photovoltaic plate.The efficiency of conversion of big area CIGS film photovoltaic board component also has the product that exceedes 14%, is the highest in all thin film photovoltaic panels;
2) low light level performance is good, the non-sun directly according to time also can produce electricity, from the experience of photovoltaic generation field actual motion, can carry at cloudy day and at dusk in the morning arch more electric energy;
3) temperature factor is low, comprises that local temperature is high or because solar radiation temperature is high, CIGS photovoltaic panel can keep higher efficiency of conversion in the time that temperature is high.Therefore under identical efficiency, CIGS photovoltaic panel is more than traditional crystal silicon photovoltaic plate electrogenesis;
4) cost is low, materials consumption is few;
5) permanent stability are good, and outdoor application is unattenuated;
6) energy pay-back period is short;
7) be applicable to the multiduty flexible photovoltaic assembly of development.
These advantages make CIGS thin-film photovoltaic panel have broad application prospects at civil area and military domain, as BIPV, large-scale low-cost power house, solar lighting light source, space and proximity space system etc.
CIGS thin-film photovoltaic panel is multi-layer film structure, generally include: substrate, back electrode, CIGS absorption layer, buffer layer, transparency conducting layer etc., wherein CIGS absorption layer is the integral part of solar energy photovoltaic panel most critical, and its preparation method has determined quality and the cost of photovoltaic panel.
The production technique that is widely used at present the compound semiconductor of photoelectric device on market is nearly all to use high-vacuum technology such as evaporation or sputter, particularly in CIGS field.But above-mentioned vacuum technique all needs to expend a large amount of costs in early investment and operational process.In addition, the vacuum-chamber dimensions of plant and instrument also can limit the output of film, further affects production efficiency.The development of antivacuum method is conducive to CIGS large-scale production.
Nanosolar company taken the lead in adopting ink printed prepare the technology of CIGS film (referring to K.Pichler, U.S. Patent number 7,122,398 and citing document).Its preparation flow is: first prepare CIGS nano particle by chemical process, then these nanoparticulate dispersed are formed to colloidal solution (being conventionally called CIGS nanometer ink), add suitable tensio-active agent to prevent nanoparticle agglomerates, in addition also add other required chemical additives of print procedure.CIGS nanometer ink forms after film printing, the solvent that needs thermal treatment to remove previously to have added, and tensio-active agent and other chemical additives, then could form homogeneous film by sintering.
Many electro-conductive materials can prepare on a large scale by electrochemical method cheaply, and preparing CIGS film with electrodip process becomes one of main direction of studying reducing costs, obtain big area CIGS film.And there are some problems by the CIGS that it is suitable that electrochemistry is prepared stoichiometric ratio at present, and in CIGS film, the mol ratio of each element is: Cu:(In+Ga): when Se ≈ 1:1:2, efficiency of conversion is higher, and the content of Ga is that 0.3 o'clock efficiency of conversion is the highest.For example: galvanic deposit CIGS needs the strict amount of controlling Cu, In, Ga, the each element of Se in solution, and accurately controls electrochemical reduction current potential, and control solution and in electrochemical deposition process, do not produce other side reactions.Even so, there is the pertinent literature of several research groups to claim and in water, electroplate out CIGS film.For example: Y.P.Fu et al.(Journal of the Electrochemical Society, 2009,156,9-E133-E138) report prepares CIGS film in the aqueous solution taking LiCl as conducting salt.Water base electrolytic solution, because the sedimentation potential of In and Ga is low, adopts more negative sedimentation potential, and the easy releasing hydrogen gas of negative electrode makes film be vesicular (evolving hydrogen reaction).In addition, they do not prepare the film that stoichiometric ratio is suitable, and in film, the content of Ga is on the low side.The compound that adds more Ga can not increase the Ga content in CIGS film in the aqueous solution.The people such as Fu point out that the compound that adds Ga in the aqueous solution causes the reduction potential of Ga more negative, Ga
3+be difficult to be reduced out at negative electrode.
The people such as Lai (Electrochimica Acta 2009,54,3004-3010) have reported a step galvanic deposit CIGS film in water-Dimethylformamide.Even in this system, because the reduction potential of Cu, In, Ga, Se quaternary element differs greatly, or be difficult to a step codeposition.In order to address this problem, Lai etc. have added complexing agent in water-Dimethylformamide, in this section of document, they equally also detailed analysis the evolving hydrogen reaction relating to above, but not the adding not and In of complexing agent Trisodium Citrate
3+, Ga
3+ion produces obvious Complex effect and changes the reduction potential of In and Ga, and it is at-0.3V ,-0.4V, and-0.5V ,-0.6V ,-0.7V ,-0.8V ,-0.9V, prepares corresponding CuIn under the current potential of-1.0V
0.21ga
0.10se
1.75, CuIn
0.40ga
0.14se
1.41, CuIn
0.35ga
0.12se
1.21, CuIn
0.42ga
0.17se
1.24, CuIn
0.43ga
0.18se
1.32, CuIn
0.47ga
0.22se
1.22, CuIn
0.62ga
0.22se
1.20, CuIn
0.57ga
0.16se
1.52.These are not the CIGS that stoichiometric ratio is suitable, all the poor In of rich Cu, Ga.
In other method, the people such as Kois (Thin Solid Films 2008,516,5948-5952) have reported that use thiocyanate-composite electrolytic solution prepares CIGS film.They have emphasized to electroplate the rear heat treated necessity of selenizing again.And their report is presented at too and electroplates in the CIGS film obtaining Ga containing quantity not sufficient.
In another method, Long and his co-worker (Journal of Physics:Conference Series2009,152,012074) have reported a step galvanic deposit CIGS film in ethanolic soln.Equally, the CIGS film obtaining after plating need to be in 550 DEG C sintering 30 minutes, and in the CIGS film of its acquisition Cu containing quantity not sufficient.
Peter etc. are reported in galvanic deposit in nonaqueous phase and prepare CIGS(" Electrochemical Deposition ofCIGS by means of Room Temperature Ionic Liquids ", Thin solid Films, 2007,515,5899-5903).This section of document description in ionic liquid, prepare Cu-In-Ga and Cu-In-Ga-Se film, after this thin film electroplating, within 30 minutes, prepare respectively 500 DEG C of selenizings CIS and the CIGS film that stoichiometric ratio is suitable.
The document of above-mentioned research galvanic deposit, mainly pays close attention to the impact of galvanic deposit liquid on electrodeposition process.CN101079454A discloses a kind of method of pulse electrodeposit CIGS semiconductor film material, the method adopts cathode pulse current potential sedimentation in substrate, to deposit the preformed layer containing copper-indium-galliun-selenium, and described pulse potential waveform is square wave, choppy sea or sine wave.CN101570871A discloses a kind of method of utilizing special burst power supply deposition copper-indium-galliun-selenium or copper-indium-gallium-selenium semiconductor film material, and the square-wave pulse that this patent adopts bells to regulate, makes preformed layer at cathode substrate substrates.Above-mentioned two kinds of methods adopt pulse wave, although it is few to have alleviated to a certain extent constant potential galvanic deposit controllable parameter, evolving hydrogen reaction is serious, the problem that thin film void rate is high; But, the method does not fundamentally solve yet because the potential difference of copper-indium-galliun-selenium is apart from causing synchronously codeposition of quaternary element, particularly the sedimentation velocity of Se is very fast, can not obtain the CIGS film that stoichiometric ratio is suitable, in electrodeposition process, generate some pure selenium balls (as the spheroid in accompanying drawing 1).It is crystal formation that these selenium clubs affect copper-indium-galliun-selenium, and also can cause has little cavity after annealing in copper-indium-galliun-selenium layer.
Summary of the invention
The object of the invention is to overcome that above-mentioned galvanic deposit prepares in CIGS thin-film technology in existing CIGS film that stoichiometric ratio is improper, formation is almost the deficiency of the selenium ball of pure selenium in coating, a kind of method that provides improved complicated wave form pulse ion liquid to plate altogether copper-indium-galliun-selenium preformed layer.The method that the present invention utilizes complicated wave form pulse ion liquid to plate altogether copper-indium-galliun-selenium preformed layer, wherein reverse impulse period is in forming copper-indium-galliun-selenium preformed layer, part selenium element strip is got back in electroplate liquid, can avoid formation selenium ball in coating, thereby forming component is even, the mutually stable copper-indium-galliun-selenium preformed layer of thing.
In order to realize foregoing invention object, the invention provides following technical scheme:
A kind of method that complicated wave form pulse ion liquid plates copper-indium-galliun-selenium preformed layer altogether, be included in electric depositing solution, obtain copper-indium-galliun-selenium preformed layer by current control pulse or voltage control pulse at cathode substrate substrates, wherein, adopt complicated wave form pulse, described complicated wave form pulse comprises that electric current and voltage all reach the direct impulse period of negative value at deposition surface, electric current and voltage deposition surface all reach on the occasion of reverse impulse period and comprise following (a)-(e) wherein one or more period, (a) stop period that curtage is null value, (b) electric current be negative value but voltage on the occasion of period, (c) electric current be on the occasion of but voltage in period of negative value, (d) voltage be negative value but electric current on the occasion of period, (e) voltage be on the occasion of but electric current in period of negative value.Described electric depositing solution is ion liquid system.In electrodeposition process, reverse impulse can, by the selenium strip depositing in relative low voltage to electric depositing solution, be avoided the pure selenium ball of formation in coating period; After current control pulse or voltage control pulse electrodeposition, near cathode substrate, in electric depositing solution, the concentration of the copper in the whole electric depositing solution of relative concentration of copper, indium, gallium, plasma selenium, indium, gallium, plasma selenium is lower, like this at stop period, copper in electric depositing solution, indium, gallium, plasma selenium concentration recover balanced, are conducive to proceed galvanic deposit.Electric current and voltage are because of contained electric capacity and resistance value in electro-deposition system, in the time of pulse, electric current and voltage have the period that positive negative value is contrary, as forwarded to during in negative value when electric current on the occasion of going back to again negative value at once, voltage be also provided with the time from negative value forward on the occasion of time electric current gone back to negative value, both just, in positive negative value contrary period, also have the function of stop period described above these periods.Described electric depositing solution is ion liquid system, and the sedimentation potential that is conducive to each element is approaching as far as possible, is conducive to obtain the preformed layer that stoichiometric ratio is suitable.
Preferably, above-mentioned complicated wave form pulse ion liquid plates in the method for copper-indium-galliun-selenium preformed layer altogether, described complicated wave form pulse comprise electric current and voltage at deposition surface be all negative value direct impulse period, electric current and voltage deposition surface all reach on the occasion of reverse impulse period, the complicated wave form impulsive condition of described current control pulse is: the working hour in direct impulse period is 3 milliseconds～1 second, current density-0.05ASD～-5ASD; The working hour in reverse impulse period is 1 millisecond～0.5 second, and current density is 0.1ASD～20ASD; Dead time is 1 millisecond～0.5 second.The complicated wave form impulsive condition of described voltage control pulse is: the working hour in direct impulse period is 3 milliseconds～1 second, voltage-0.5V～-8.0V; The working hour in reverse impulse period is 1 millisecond～0.5 second, and voltage is 0.1V～50.0V; Dead time is 1 millisecond～0.5 second.Under above-mentioned impulsive condition, when galvanic deposit forms copper-indium-galliun-selenium preformed layer, be conducive to selenium element strip, to electric depositing solution, can obtain the CIGS film that stoichiometric ratio is suitable, avoid forming selenium ball in coating.
Above-mentioned complicated wave form pulse ion liquid plates in the method for copper-indium-galliun-selenium preformed layer altogether, and in electric depositing solution, the concentration of copper, indium, gallium, plasma selenium is respectively 0.1mM-50mM, 0.1mM-60mM, 0.1mM-80mM, 0.1mM-50mM.
Described ionic liquid is made up of choline chloride 60 and urea, and choline chloride 60 is 1:0.5 ~ 1:5 than the weight ratio of urea, is preferably 1:2.
Above-mentioned complicated wave form pulse ion is coated with altogether standby preformed layer ionic liquid and plates altogether in the method for copper-indium-galliun-selenium preformed layer, vitriol, acetate, Bromide, fluoride salt, chlorate, iodized salt, hydroxide salt, nitridation salt, oxalate, Citrate trianion, phosphoric acid salt, tungstate, hydrate or their combination that in ionic liquid, the kind of cupric ion comprises copper.
Above-mentioned complicated wave form pulse ion liquid plates in the method for copper-indium-galliun-selenium preformed layer altogether, vitriol, acetate, Bromide, fluoride salt, chlorate, iodized salt, hydroxide salt, nitridation salt, oxalate, Citrate trianion, phosphoric acid salt, tungstate, hydrate or their combination that in ionic liquid, the kind of gallium ion comprises gallium.
Above-mentioned complicated wave form pulse ion liquid plates in the method for copper-indium-galliun-selenium preformed layer altogether, vitriol, acetate, Bromide, fluoride salt, chlorate, iodized salt, hydroxide salt, nitridation salt, oxalate, Citrate trianion, phosphoric acid salt, tungstate, hydrate or their combination that in ionic liquid, the kind of indium ion comprises indium.
Above-mentioned complicated wave form pulse ion liquid plates in the method for copper-indium-galliun-selenium preformed layer altogether, vitriol, acetate, Bromide, fluoride salt, chlorate, iodized salt, hydroxide salt, nitridation salt, oxalate, Citrate trianion, phosphoric acid salt, tungstate, hydrate or their combination that in ionic liquid, the kind of plasma selenium comprises selenium.
Above-mentioned complicated wave form pulse ion liquid plates in the method for copper-indium-galliun-selenium preformed layer altogether, any one in the polymkeric substance that the kind of conductive substrates comprises conductive polymers, covering metal, the polymkeric substance that covers transparency conducting layer, the glass that covers ITO, the polymkeric substance that covers ITO, the pottery that covers conductive layer, metal, amorphous semiconductor material, crystal semiconductor material, polycrystalline semiconductor material or their combination.
Above-mentioned complicated wave form pulse ion liquid plates in the method for copper-indium-galliun-selenium preformed layer altogether, and in electric depositing solution, all or part of cupric ion is by entering electric depositing solution after anodic oxidation.
Above-mentioned complicated wave form pulse ion liquid plates in the method for copper-indium-galliun-selenium preformed layer altogether, and in electric depositing solution, all or part of gallium ion is by entering electric depositing solution after anodic oxidation.
Above-mentioned complicated wave form pulse ion liquid plates in the method for copper-indium-galliun-selenium preformed layer altogether, and in electric depositing solution, all or part of indium ion is by entering electric depositing solution after anodic oxidation.
Above-mentioned complicated wave form pulse ion liquid plates in the method for copper-indium-galliun-selenium preformed layer altogether, and in electric depositing solution, all or part of plasma selenium is by entering electric depositing solution after anodic oxidation.
The method that adopts above-mentioned complicated wave form pulse ion liquid to plate altogether copper-indium-galliun-selenium preformed layer, it is integral prefabricated layer thickness more than 20% that described reverse impulse participates in the thickness of deposition preformed layer period.Contriver finds, in electrochemical deposition process, the preformed layer that reverse impulse prepares period is integral prefabricated layer thickness 20% when above, can obtain that composition is even, the mutually stable copper-indium-galliun-selenium preformed layer of thing.
Compared with prior art, beneficial effect of the present invention:.
Prepare in the process of copper-indium-galliun-selenium at electrochemical deposition, because four kinds of elements of copper-indium-galliun-selenium exist potential difference, the complexity difference of each element electrolysis, synchronously codeposition of four kinds of elements, particularly Se deposits under relatively low voltage, thereby be difficult to obtain the CIGS film that stoichiometric ratio is suitable, in electrodeposition process, generate some selenium balls (as the spheroid in accompanying drawing 1).These selenium ball impact copper-indium-galliun-seleniums are crystal formation, and also can cause has little cavity after annealing in copper-indium-galliun-selenium layer.Complicated wave form pulse ion liquid of the present invention plates in copper-indium-galliun-selenium preformed layer method altogether, in the process of electrochemical deposition, adopt reverse impulse, in preparing copper-indium-galliun-selenium preformed layer, can to electric depositing solution, avoid forming selenium ball in coating by depositing selenium strip faster, stop period copper, indium, gallium, plasma selenium concentration in electric depositing solution recover balanced, be conducive to proceed galvanic deposit, thereby forming component is even, the mutually stable copper-indium-galliun-selenium preformed layer of thing.
Contriver finds, in electrochemical deposition process, the preformed layer that reverse impulse prepares period is integral prefabricated layer thickness 20% when above, can reduce near copper-indium-galliun-selenium layer and metal level interface formation empty.Further, the preferred impulsive condition of contriver, all carry out galvanic deposit period at the direct impulse of negative value at electric current and voltage at deposition surface, electric current and voltage deposition surface all on the occasion of reverse impulse carry out strip period, stop period makes the ionic concn in electrodeposit liquid recover balanced.Under above-mentioned impulsive condition effect, when galvanic deposit forms copper-indium-galliun-selenium preformed layer, be conducive to selenium element strip to electric depositing solution other elements of strip hardly, can obtain the CIGS film that stoichiometric ratio is suitable, avoid forming selenium ball in coating.Further, electrochemical deposition method of the present invention preferably carries out in ionic liquid system, and it is approaching as far as possible that ionic liquid system is conducive to the sedimentation potential of each element, is conducive to obtain the preformed layer that stoichiometric ratio is suitable.
Brief description of the drawings:
Fig. 1 is the electron-microscope scanning figure of copper-indium-galliun-selenium preformed layer in prior art, and in figure, ball is selenium ball.
Fig. 2 is embodiment 1 pulse current density and corresponding voltage change figure.
Fig. 3 is the configuration of surface figure of the embodiment 1 of scanning electronic microscope acquisition.
Fig. 4 is embodiment 2 pulsed voltages and corresponding current density change figure.
Fig. 5 is the configuration of surface figure of the embodiment 2 of scanning electronic microscope acquisition.
Fig. 6 is comparative example 1 continuous current current density and corresponding voltage change figure.
Fig. 7 is the configuration of surface figure of the comparative example 1 of scanning electronic microscope acquisition.
Fig. 8 is comparative example 2 constant voltages and corresponding current density change figure.
Fig. 9 is the configuration of surface figure of the comparative example 2 of scanning electronic microscope acquisition.
Embodiment
Below in conjunction with test example and embodiment, the present invention is described in further detail.But this should be interpreted as to the scope of the above-mentioned theme of the present invention only limits to following embodiment, all technology realizing based on content of the present invention all belong to scope of the present invention.
The method that the complicated wave form pulse ion liquid that the present embodiment is enumerated plates copper-indium-galliun-selenium preformed layer altogether, is included in electric depositing solution, adopts complicated wave form pulse, obtains copper-indium-galliun-selenium preformed layer by impulse of current at cathode substrate substrates.Described cathode substrate is soda-lime glass, has covered the conduction molybdenum layer that one deck forms after with vacuum splashing and plating on it.Wherein, described complicated wave form pulse comprise electric current and voltage deposition surface all direct impulse period, electric current and the voltage of negative value deposition surface all on the occasion of reverse impulse period and stop period.Pulse current density and corresponding voltage change are shown in Fig. 2, and the current density of pulse and working hour are in table 1.
In the present embodiment, electric depositing solution is ion liquid system, and ion liquid system is made up of urea and choline chloride 60, and the weight ratio of choline chloride 60 and urea is 1:0.5, and in ion liquid system, the content of copper, indium, gallium, plasma selenium and source are in table 3.Electrochemical deposition setting comprises as the platinized platinum of anode, the power supply of reverse impulse can be provided as the platinum filament of reference electrode and one.When electrochemical deposition with current control, the variation of measurement simultaneously and record current and relevant voltage.
The CIGS preformed layer configuration of surface preparing according to the method for the present embodiment is carried out electron microscope scanning, and as shown in Figure 3, CIGS surface is without ball-like structure, and X-ray energy spectrum has shown that the content of selenium is 50.8%, and overall composition meets the requirement of copper-indium-galliun-selenium preformed layer.
Embodiment 2
The method that the complicated wave form pulse ion liquid that the present embodiment is enumerated plates copper-indium-galliun-selenium preformed layer altogether, is included in electric depositing solution, adopts complicated wave form pulse, obtains copper-indium-galliun-selenium preformed layer by voltage pulse at cathode substrate substrates.Described cathode substrate is the glass substrate of plating Mo and Cu.Wherein, described complicated wave form pulse comprise electric current and voltage deposition surface all direct impulse period, electric current and the voltage of negative value deposition surface all on the occasion of complicated wave form pulse period and stop period.Pulsed voltage and corresponding curent change are shown in Fig. 4, and pulsed voltage and working hour are in table 2.
In the present embodiment, electric depositing solution is ion liquid system, and described ion liquid system is made up of urea and choline chloride 60, and the weight ratio of choline chloride 60 and urea is 1:1, and in ionic system, the content of copper, indium, gallium, plasma selenium and source are in table 3.Electrochemical deposition setting comprises as the platinized platinum of anode, the power supply of reverse impulse can be provided as the platinum filament of reference electrode and one.When electrochemical deposition with current control, the variation of measurement simultaneously and recording voltage and respective electrical flow density.
The CIGS preformed layer configuration of surface preparing according to the method for the present embodiment is carried out electron microscope scanning, and as shown in Figure 5, CIGS surface is without ball-like structure, and X-ray energy spectrum has shown that the content of selenium is 51.7%, and overall composition meets the requirement of copper-indium-galliun-selenium preformed layer.
Comparative example
Comparative example 1
The method of plating altogether copper-indium-galliun-selenium preformed layer according to embodiment 1 complicated wave form pulse ion liquid.Different with embodiment 1 in it is that described electrochemical deposition is continuous current, and the current density of galvanostatic deposition and corresponding voltage change are shown in Fig. 6, and the current density of continuous current is in table 1, and all the other conditions are with embodiment 1.
The CIGS preformed layer configuration of surface preparing according to this comparative example is carried out electron microscope scanning, as shown in Figure 7, CIGS surface has been full of a lot of ball volt structures, lying prostrate from ball the content that the X-ray energy spectrum obtaining shown selenium is 98%, the content of the structure selenium on spherical side is 44%, and other composition comprises copper, indium and gallium.
Comparative example 2
The method of plating altogether copper-indium-galliun-selenium preformed layer according to embodiment 2 complicated wave form pulse ion liquid.Different with embodiment 2 in it is that described electrochemical deposition is constant voltage, and the voltage of constant voltage and corresponding current density change are shown in Fig. 8, and the voltage of constant voltage deposition is in table 2, and all the other conditions are with embodiment 2.
The CIGS preformed layer configuration of surface preparing according to this comparative example is carried out electron microscope scanning, as shown in Figure 9, CIGS surface has been full of a lot of ball volt structures, lying prostrate from ball the content that the X-ray energy spectrum obtaining shown selenium is 86%, the content of the structure selenium on spherical side is 38%, and other composition comprises copper, indium and gallium.
The isopulse that the complicated wave form pulse that table 1 embodiment 1 uses and comparative example 1 are used
The isopulse that the complicated wave form pulse that table 2 embodiment 2 uses and comparative example 2 are used
The content of copper, indium, gallium, selenium and source in table 3 electrochemical deposition liquid
Claims (12)
1. the method that complicated wave form pulse ion liquid plates copper-indium-galliun-selenium preformed layer altogether, be included in electric depositing solution, obtain copper-indium-galliun-selenium preformed layer by current control pulse or voltage control pulse at cathode substrate substrates, it is characterized in that: described current control pulse or voltage control pulse adopt complicated wave form pulse, described complicated wave form pulse comprises that electric current and voltage are all the direct impulse period of negative value at deposition surface, electric current and voltage deposition surface be all on the occasion of reverse impulse period and comprise following (a)-(e) wherein one or more period, (a) stop period that curtage is null value, (b) electric current be negative value but voltage on the occasion of period, (c) electric current be on the occasion of but voltage in period of negative value, (d) voltage be negative value but electric current on the occasion of period, (e) voltage be on the occasion of but electric current in period of negative value.
2. the method that complicated wave form pulse ion liquid according to claim 1 plates copper-indium-galliun-selenium preformed layer altogether, is characterized in that: described electric depositing solution is ion liquid system.
3. the method that complicated wave form pulse ion liquid according to claim 1 plates copper-indium-galliun-selenium preformed layer altogether, it is characterized in that, described complicated wave form pulse comprise electric current and voltage at deposition surface be all negative value direct impulse period, electric current and voltage deposition surface all reach on the occasion of reverse impulse period and stop period, the complicated wave form impulsive condition of described current control pulse is: the working hour in direct impulse period is 3 milliseconds～1 second, current density-0.05ASD～-5ASD; The working hour in reverse impulse period is 1 millisecond～0.5 second, and current density is 0.1ASD～20ASD; Dead time is 1 millisecond～0.5 second.
4. the method that complicated wave form pulse ion liquid according to claim 1 plates copper-indium-galliun-selenium preformed layer altogether, it is characterized in that, described complicated wave form pulse comprise electric current and voltage at deposition surface be all negative value direct impulse period, electric current and voltage deposition surface all reach on the occasion of reverse impulse period and stop period, the complicated wave form impulsive condition of described voltage control pulse is: the working hour in direct impulse period is 3 milliseconds～1 second, voltage-0.5V～-8.0V; The working hour in reverse impulse period is 1 millisecond～0.5 second, and voltage is 0.1V～50.0V; Dead time is 1 millisecond～0.5 second.
5. the method that complicated wave form pulse ion liquid according to claim 1 plates copper-indium-galliun-selenium preformed layer altogether, it is characterized in that, in described electric depositing solution, the concentration of copper, indium, gallium, plasma selenium is respectively 0.1mM ~ 50mM, 0.1mM-60mM, 0.1mM-80mM, 0.1mM-50mM.
6. the method that complicated wave form pulse ion liquid according to claim 1 plates copper-indium-galliun-selenium preformed layer altogether, is characterized in that, described ion liquid system is made up of urea and choline chloride 60, and the weight ratio of choline chloride 60 and urea is 1:0.5 ~ 1:5.
7. the method that complicated wave form pulse ion liquid according to claim 6 plates copper-indium-galliun-selenium preformed layer altogether, is characterized in that, the weight ratio of choline chloride 60 and urea is 1:2.
8. the method that complicated wave form pulse ion liquid according to claim 5 plates copper-indium-galliun-selenium preformed layer altogether, is characterized in that, in electric depositing solution, all or part of cupric ion is by entering electric depositing solution after anodic oxidation.
9. the method that complicated wave form pulse ion liquid according to claim 5 plates copper-indium-galliun-selenium preformed layer altogether, is characterized in that, in electric depositing solution, all or part of gallium ion is by entering electric depositing solution after anodic oxidation.
10. the method that complicated wave form pulse ion liquid according to claim 5 plates copper-indium-galliun-selenium preformed layer altogether, is characterized in that, in electric depositing solution, all or part of indium ion is by entering electric depositing solution after anodic oxidation.
The method that 11. complicated wave form pulse ion liquid according to claim 5 plate copper-indium-galliun-selenium preformed layer altogether, is characterized in that, in electric depositing solution, all or part of plasma selenium is by entering electric depositing solution after anodic oxidation.
The 12. copper-indium-galliun-selenium preformed layers of preparing according to the arbitrary electrochemical deposition method described in claim 1～11, is characterized in that: it is integral prefabricated layer thickness more than 20% that described complicated wave form pulse participates in the thickness of deposition preformed layer period.
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