CN104851931B - Cadmium telluride diaphragm solar battery and its manufacture method with gradient-structure - Google Patents
Cadmium telluride diaphragm solar battery and its manufacture method with gradient-structure Download PDFInfo
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Abstract
The invention discloses a kind of cadmium telluride diaphragm solar battery with gradient-structure and its manufacture method, the CdTe absorbed layers that the battery includes in the pn-junction formed by CdTe absorbed layers and CdS Window layers, the pn-junction of the cadmium telluride diaphragm solar battery are CdxTeyMultilayered and graded structure with Graded band-gap, wherein 0≤x≤1,0≤y≤1.The gradient-structure has wider energy spectrum, can separate and catch free electron, under the exciting of sunshine, forms larger current and improves the efficiency of thin-film solar cells.The gradient-structure avoids abnormal growth and hole and the formation in crack of crystal grain, be prepared for densification, grain size is uniform, energy gap matching high-quality film, meanwhile, the gradient-structure is conducive to fully absorbing sunshine.Thus, further increase the efficiency of cadmium telluride diaphragm solar battery.
Description
Technical field
The present invention relates to solar cell and thin-film solar cells and its manufacture method with gradient-structure, particularly
Cadmium telluride diaphragm solar battery structure and its manufacture method with gradient-structure.
Background technology
Since French scientist AE.Becquerel 1839 find opto-electronic conversion phenomenon after, 1883 first with
Semiconductor selenium is born for the solar cell of substrate.Nineteen forty-six Russell obtains the patent of first solar cell
(US.2,402,662), its photoelectric transformation efficiency is only 1%.Until 1954, the research of AT＆T Labs was just found that doping
Silica-base material there is high photoelectric transformation efficiency.This research is laid a good foundation for modern sun energy battery industry.1958
Year, Haffman Utilities Electric Co.s of the U.S. have loaded onto first piece of solar panel for the satellite in the U.S., and its photoelectric transformation efficiency is about
6%.From this, the solar cell research and production of monocrystalline silicon and polycrystalline silicon substrate have quick development, solar energy in 2006
The yield of battery has reached 2000 megawatts, and the photoelectric transformation efficiency of monocrystaline silicon solar cell reaches 24.7%, commercial product
22.7% is reached, the photoelectric transformation efficiency of polysilicon solar cell reaches 20.3%, and commercial product reaches 15.3%.
On the other hand, the Zhores Alferov of the Soviet Union in 1970 have developed the race of high efficiency III-V of first GaAs base
Solar cell.Due to prepare III-V race's thin-film material key technology MOCVD (metal organic chemical vapor deposition) until
Just successfully researched and developed within 1980 or so, the applied solar energy Battery Company in the U.S. was successfully applied to the technology in 1988 and prepared
Photoelectric transformation efficiency is III-V race's solar cell of 17% GaAs bases.Thereafter, III-V race's material by substrate of GaAs
Doping techniques, the technology of preparing of plural serial stage solar cell obtained extensive research and development, its photoelectric transformation efficiency
19% was reached in 1993,24% is reached within 2000,26% is reached within 2002, reaches within 2005 28%, reach 30% within 2007.
2007, big III-V race solar cell company Emcore and SpectroLab in the U.S. two produced the race's sun of high efficiency III-V
Energy commercial product, its photoelectric conversion rate is up to 38%, and this two company occupies the 95% of global III-V race's solar cell market,
Nearest American National Energy Research Institute announces, they successfully have developed the plural serial stage that its photoelectric transformation efficiency is up to 50%
III-V race's solar cell.Because the substrate of this kind of solar cell is expensive, equipment and process costs are high, are mainly used in boat
The fields such as sky, space flight, national defence and military project.
External solar cell research and production, can substantially be divided into three phases, that is, have three generations's solar cell.
First generation solar cell, substantially using the solar cell of monocrystalline silicon and the single constituent element of polycrystalline silicon substrate as generation
Table.Only pay attention to improve photoelectric transformation efficiency and large-scale production, there is high energy consumption, labour intensive, unfriendly to environment
The problems such as with high cost, its price for producing electricity is about the 2 of coal electricity~3 times；Until, the production of first generation solar cell in 2014
Amount still accounts for the 80-90% of global solar battery total amount.
Second generation solar cell is thin-film solar cells, is the new technology grown up in recent years, it pays attention to
The energy consumption and process costs in production process are reduced, brainstrust is called green photovoltaic industry.With monocrystalline silicon and the polysilicon sun
Energy battery is compared, and the consumption of its film HIGH-PURITY SILICON is its 1%, meanwhile, low temperature (about 200 DEG C or so) plasma enhanced
Vapour deposition deposition technique is learned, electroplating technology, printing technology is extensively studied and is applied to the life of thin-film solar cells
Production.Due to the glass using low cost, stainless steel thin slice, macromolecule substrate is substantially reduced as baseplate material and low temperature process
Production cost, and be conducive to large-scale production.The material of the successful thin-film solar cells researched and developed is at present：CdTe,
Its photoelectric transformation efficiency is 16.5%, and commercial product is about 12% or so；CulnGaSe (CIGS), its photoelectric transformation efficiency is
19.5%, commercial product is 12% or so；Non-crystalline silicon and microcrystal silicon, its photoelectric transformation efficiency are 8.3~15%, and commercial product is
7~12%, in recent years, due to the research and development of the thin film transistor (TFT) of LCD TV, non-crystalline silicon and microcrystalline silicon film technology have considerable
Development, and be applied to silicon-based film solar cells.Focus around thin-film solar cells research is, exploitation efficiently,
Inexpensive, long-life photovoltaic solar cell.They should have following feature：Low cost, high efficiency, long-life, material come
Source is abundant, nontoxic, and scientists relatively have an optimistic view of amorphous silicon thin-film solar cell.The thin film solar electricity of lion's share is accounted at present
Pond is non-crystal silicon solar cell, usually pin structure batteries, and Window layer is the P-type non-crystalline silicon of boron-doping, then deposits one layer not
The i layers of doping, the N-type non-crystalline silicon of redeposited one layer of p-doped, and plated electrode.Brainstrust is, it is expected that due to thin-film solar cells tool
There is a low cost, high efficiency, the ability of large-scale production, at following 10~15 years, thin-film solar cells will turn into complete
The main product of ball solar cell.
Amorphous silicon battery typically using PECVD (Plasma Enhanced Chemical Vapor Deposition-etc.
Ion enhanced chemical vapor deposition) method make the gases such as high purity silane decompose deposition.Such a manufacture craft, Ke Yi
It is continuous in production to be completed in multiple vacuum deposition chamber, to realize production in enormous quantities.Due to deposition decomposition temperature it is low, can glass,
Stainless steel plate, ceramic wafer, deposition film on flexible plastic sheet, it is easy to which large area metaplasia is produced, cost is relatively low.Make on a glass substrate
The structure of standby amorphous silica-based solar cell is：Glass/TCO/p-a-SiC/i-a-Si/n-a-Si/TCO, in stainless steel
The structure of the amorphous silica-based solar cell prepared on substrate is：SS/ZnO/n-a-Si/i-a-Si/p-na-Si/ITO.
Internationally recognized amorphous silicon/microcrystalline silicon tandem solar cell is the next-generation technology of silicon-base thin-film battery, is to realize
The important technology approach of high efficiency, low cost thin-film solar cells, is the new industrialization direction of hull cell.Microcrystalline silicon film is certainly
Use hydrogen plasma chemical vapor deposition since 600 DEG C prepare first from nineteen sixty-eight by Veprek and Maracek, people start
There is Preliminary study to its potential premium properties, until 1979, Japanese Usui and Kikuchi were by using high hydrogen
Silicon than process and low-temperature plasma enhancing chemical vapour deposition technique, prepare doped microcrystalline silicon, people are just gradually right
Microcrystalline silicon materials and its application in solar cells are studied., Switzerland in 1994M.J.Williams
Proposed first using microcrystal silicon as bottom battery with M.Faraji team, non-crystalline silicon is the concept of the laminated cell of top battery, this electricity
Pond combines the good advantage of long-wave response and stability of non-crystalline silicon good characteristic and microcrystal silicon.Mitsubishi heavy industrys in 2005 and
The amorphous silicon/microcrystalline silicon tandem battery component sample efficiencies of Zhong Yuan chemical companies respectively reach 11.1% (40cm × 50cm) and
13.5% (91cm × 45cm).Japanese Sharp company in September, 2007 realizes amorphous silicon/microcrystalline silicon tandem solar cell industry
Produce (25MW, efficiency 8%-8.5%), European Oerlikon (Oerlikon) company in September, 2009 announces its amorphous/crystallite lamination
The solar cell exhibition that solar cell laboratory highest conversion efficiency is opened up to 11.9%, at 2010 6 in Yokohama
On " PVJapan2010 ", Applied Materials (AMAT) announce that the conversion efficiency of 0.1m × 0.1m modules has reached 10.1%,
The conversion efficiency of 1.3m × 1.1m modules has reached 9.9%.The maximally effective approach of battery efficiency is improved to be to try to improve battery
Efficiency of light absorption.It is inevitable approach using low bandgap material for silica-base film.The arrowband used such as Uni-Solar companies
Gap material is a-SiGe (amorphous silicon germanium) alloy, their a-Si/a-SiGe/a-SiGe three-knot laminated batteries, small area battery
(0.25cm2) efficiency reaches 15.2%, stabilization efficiency is up to 13%, 900cm2Component efficiency is up to 11.4%, and stabilization efficiency reaches
10.2%, product efficiency reaches 7%-8%.
For thin-film solar cells, unijunction, the silion cell without optically focused, in theory maximum photoelectric conversion
Efficiency is 31% (Shockley-Queisser limitations).According to the order of band-gap energy reduction, the silicon without optically focused of binode
Battery, maximum electricity conversion rises to 41% in theory, and three knots can reach 49%.Therefore, multi-knot thin film is developed
Solar cell is the important channel for lifting solar battery efficiency.For cadmium telluride diaphragm solar battery, with cadmium telluride phase
The fusing point of the high or low band gap material of matching is very low and unstable, it is difficult to form many efficient series-connected solar cells of knot.For
CIGS thin film solar cell, is difficult to prepare with the high or low band gap material that CIGS matches, and is not easy to form many knots efficiently string
Join solar cell.For silicon-based film solar cells, the band gap of crystalline silicon and non-crystalline silicon is 1.1eV and 1.7eV, and is received
The band gap of rice silicon changes according to the big I of crystallite dimension between 1.1eV and 1.7eV.Si based compounds, such as crystal Si1-
XGex band gap (0≤X≤1) can change to 0.7eV according to Ge concentration from 1.1eV, and amorphous SiGe can be 1.4, and Amorphous GaN is about
1.95eV, this combination exactly matches with the spectrum of the sun.
On the other hand, luminous energy how is fully absorbed, the electricity conversion of solar cell is improved, allows as many as possible
Electronic energy be optically excited and be changed into electric energy, so, the level-density parameter of battery material and few defect are of crucial importance.From
For technological layer, the technological difficulties of thin film deposition ensure the high-quality and uniform of film while being to realize high speed deposition
Property, because film crystallite dimension, the quality and uniformity of the base material of Growing Process of Crystal Particles and growth all to film have strongly
Influence, so as to influence whole battery performance to show.In film Growing Process of Crystal Particles, due to the abnormal growth of crystal grain, cause
Grain size is uneven, easily forms hole and crack.The hole and crack being full of in film add the compound of carrier,
And cause leakage current, seriously reduce Voc and FF values.Therefore, this technical barrier is solved, is to prepare the efficient film sun
The important channel of energy battery.
We in patent ZL200910043930-4, ZL200910043931-9 and ZL200910226603-2 from
Technical elements, have manufactured efficient a-Si/ μ C-Si, and a-Si/nC-Si/ μ C-Si binodes and three knot silicon-based film solars
Battery, high density (HD) and hyperfrequency (VHF)-PECVD technique have been developed and have been used for high-quality, the a-Si of large scale, a-
SiGe, nC-Si, μ C-Si, A-SiC thin film deposition.Using a-SiC as Window layer, and p-type doping Si-rich silicon oxide film is used
Central reflector layer has been used for increasing a-Si/ μ C-Si binodes and a-Si/nC- between top a-Si and bottom μ c-Si batteries
The efficiency of the knot silicon-based film solar cells of Si/ μ C-Si tri-.High-quality B doping ZnOx CVD process optimizations, improve it
Mist degree and electrical conductivity, and have studied other light capture techniques.The laboratory sample efficiency of three knot silicon-based film solar cells
15% can be reached, commercialized a-Si/ μ C-Si (1.1 meters x1.3 meters) sun of 10% and the above is more than with stabilization efficiency
It is prepared by energy battery component.
The application is on patent ZL200910043930-4, ZL200910043931-9 and ZL200910226603-2 basis
It is upper to continue to study, it is desirable to provide a kind of cadmium telluride diaphragm solar battery and its manufacture method with gradient-structure.
Cadmium telluride (CdTe) thin-film solar cells is a kind of film based on p-type CdTe and n-type CdS hetero-junctions
Solar cell.In recent years, CdTe thin film solar cell is with its optoelectronic transformation efficiency height, low production cost, high stability, absorption
The advantages of spectral width, life cycle terminate rear recyclable, extremely China and foreign countries are paid close attention to.
CdTe thin film solar cell is sequentially depositing plural layers on glass or other flexible substrates and constituted
Photovoltaic device.The CdTe thin film solar cell of general standard is made up of five-layer structure, as shown in Figure 1, wherein the direction of arrow
For direction of illumination.
(English name is Transparent to the transparent conductive oxide that first layer is deposited in transparent substrates
AndConductive Oxide, abbreviation TCO) layer, it is main to play printing opacity and conduction；The second layer is CdS Window layers, the layer
For n-type semiconductor；Third layer is CdTe absorbed layers, is p-type semiconductor, this layer and the n-type CdS formation p-n junctions of Window layer, the 4th
Layer is back contacts (English name the is back contact) layer deposited on CdTe absorbed layers, and the effect of this layer is reduction
CdTe and metal electrode contact berrier, make metal electrode and CdTe formation Ohmic contacts；Finally it is deposited on back contact
It is back electrode (English name is back electrode) layer, the layer is metal material layer, is connected with tco layer by external circuit,
For electric current to be drawn.CdTe thin film solar cell with said structure operationally, when there is light to wear to penetrate transparent substrates and
Tco layer is irradiated to p-n junction, and photon energy is when being more than p-type CdTe energy gaps, the electrons gain energy jump in absorbed layer valence band
Conduction band is adjourned, while producing hole in valence band, electron-hole pair, the nonequilibrium carrier of generation can be produced near p-n junction
Drifted about because the built in field that n-type semiconductor to p-type semiconductor is formed is acted on to space-charge region two ends so as to produce photoproduction electricity
Gesture.When p-n junction and external circuit are turned on, electric current occurs in circuit.
The content of the invention
The technical problem to be solved in the present invention is, for the thin-film material and solar spectral energy gap of prior art presence
The problem of defect match somebody with somebody, produced in crystal grain formation and growth course, and how to fully absorb sunshine and improve photoelectric conversion
Efficiency, proposes cadmium telluride diaphragm solar battery and its manufacture method with gradient-structure.
To achieve the above object, the technical scheme is that：
A kind of cadmium telluride diaphragm solar battery with gradient-structure, including by CdTe absorbed layers and CdS Window layers institute
CdTe absorbed layers in the pn-junction of formation, the pn-junction of the cadmium telluride diaphragm solar battery are CdxTeyGradient-structure, wherein 0
≤ x≤1,0≤y≤1, the gradient-structure is the sandwich construction with Graded band-gap；The CdxTeyGradient-structure energy gap exists
Between 1.6eV-1.3eV, from the first floor to last layer from high energy gap layer to low energy gap layer even transition, and between two layers of arbitrary neighborhood
Energy gap difference is between 0.01-0.1eV.
The CdxTeyGradient-structure is preferably selected from the one or more in following three kinds of forms：
(1) CdxTeyGradient-structure is by Cd miscellaneous Cu Erbium-dopedxTeyLayer even transition arrive by it is other so that energy gap reduction
Material doping CdxTeyLayer form, it is described it is other cause energy gap reduction materials in Zn, Hg, Se, Mg and S one
Plant or several；Wherein Cu atom doped amount is from 25% even transition to 0%, and the atom of other materials that energy gap is reduced is mixed
Miscellaneous amount is from 0% even transition to 25%；
(2) CdxTeyGradient-structure gradually increases for Cd content, the form that Te content is gradually decreased；
(3) CdxTeyGradient-structure is gradually increased to 3 microns of form for CdTe crystallite dimension from 10nm.
Three of the above form is the Cd to form energy gap changexTeyThree kinds of modes of gradient-structure, can be one of which shapes
Energy gap change or wherein several forms also result in energy gap change caused by formula.
The CdxTeyThe gross thickness of gradient-structure is preferably between 0.1 micron to 3 microns.
The CdxTeyThe energy gap of gradient-structure is uniform according to the form preferably according to energy gap difference between 0.01-0.05eV
Reduction.
The CdxTeyBetween the thickness of each transition zone is preferably 1nm-100nm in gradient-structure, it is more preferably
1nm-10nm。
The preparation method of the cadmium telluride diaphragm solar battery with gradient-structure, it is described with gradient-structure
CdTe absorbed layers are prepared using co-evaporation method, and concrete technology control parameter includes：First substrate back is removed before preparing with concentrated hydrochloric acid
CdS layer, then dilute hydrochloric acid solution wash 3-5 seconds, then cleaned and dried with deionized water；Substrate is loaded in behind settling chamber,
At a temperature of 380 DEG C -420 DEG C, in CO, CO2Or H2Atmosphere under, pre-process 15-20 minutes；When being cooled to 150 DEG C -200 DEG C,
The vacuum of reative cell is extracted into 0.01-0.03 Torrs of pressure, then passes to helium, when reaching 10-20 Torrs of pressure, starts plating slow
Layer film is rushed, then substrate temperature is raised to as 600 DEG C -650 DEG C, CdTe and Zn, Hg and the miscellaneous CdTe graphite boat evaporation source temperature of S Erbium-doped
Spend for 650 DEG C -750 DEG C, prepared by 1100 DEG C -1400 DEG C of Cu raw graphite boats source temperature carrys out cadmium telluride gradient-structure, often plates
A complete tunic, the oxide or CdTe particulates loosely adhered to is removed with dry nitrogen.
After CdTe gradient-structures deposition is completed, made annealing treatment using caddy：CdTe gradient-structures are placed in one
In the 60%-80% methanol solutions of individual saturation caddy；The substrate of CdTe gradient-structures is at 50 DEG C -70 DEG C by immersion 15 minutes
Afterwards, the dry N of taking-up2Drying, is put into oven in 100sccm helium stream and 25sccm O2Under air-flow and 360 DEG C-
40-45 minutes are toasted at a temperature of 450 DEG C to be cooled to after 45 DEG C -50 DEG C, are rinsed with deionized water and are removed excessive cadmium.
The present invention is further explained and illustrated below：
The cadmium telluride diaphragm solar battery with gradient-structure includes unijunction or ties cadmium telluride diaphragm solar more
Battery.
For cadmium telluride diaphragm solar battery, its gradient-structure is combined by following match materials and formed：CdxTey
(1.4-1.6eV)/Cu, Zn, Hg and/or S Erbium-doped miscellaneous CdxTey(1.3-1.5eV) (1 >=x >=0, y=2-x) by changing Cu,
Zn, Hg and the S miscellaneous amounts of Erbium-doped (the miscellaneous amounts of Erbium-doped from 0 to 25%), x and y ratio and grain size adjust telluride cadmium material
Energy gap is matched.For Cu doping, when Cu dopings from 0 increase to 25%, the crystal structure of cadmium telluride is by CdTe forms six
Square structure is changed into the hexagonal structure of Cu2Te forms, and its optical band gap increases to 1.62 electron-volts by 1.48 electron-volts.For
For S doping, work as CdTe1-xSxMolecular formula in, when S doping from 0 increases to 25%, its optical band gap is by 1.51 electronics
Volt is reduced to 1.41 electron-volts.In addition, the doping of the element such as experiment proof Zn, Hg, Mg, Se can cause CdTe optical ribbon
Gap (or energy gap) diminishes.And growing up with CdTe crystal grain, its energy gap also has the trend diminished.
Many knots of the present invention have in the thin-film solar cells of gradient-structure, are pushed up using the gradient-structure of wide gap material
Electricity knot, electric energy is converted into by the luminous energy of short wavelength；Bottom electricity knot is done using the gradient-structure of arrowband material, can be by speciality wavelength luminous energy
It is converted into electric energy.Due to more taking full advantage of the spectral domain of sunlight, many thin-film solar cells of the knot with gradient-structure have
Higher photoelectric transformation efficiency.Gradient-structure change in elevation is determined by the energy gap difference being made between material, passes through its material that matches
The energy gap size of material is adjusted.Every grade of gradient-structure varying width can be adjusted by forming the thickness of same gap material.
Compared with prior art, advantage of the invention is that:
Cadmium telluride diaphragm solar battery of the present invention with gradient-structure can separate and catch free electron,
Under the exciting of sunshine, form larger current and improve the efficiency of thin-film solar cells.The gradient-structure avoids crystal grain
Abnormal growth and hole and crack formation, be prepared for densification, grain size is uniform, energy gap matching it is high-quality
Film, meanwhile, the gradient-structure is conducive to fully absorbing sunshine.Thus, further increase thin film solar electricity
The efficiency in pond.
Brief description of the drawings
Fig. 1 is the structural representation of existing CdTe thin film solar cell.
Fig. 2 is the cadmium telluride diaphragm solar battery structural representation with doping gradient structure；
Fig. 3 is the cadmium telluride diaphragm solar battery structural representation with composition variable gradient structure；
Fig. 4 is the cadmium telluride diaphragm solar battery structural representation with crystallite dimension variable gradient structure；
Fig. 5 is the cadmium telluride diaphragm solar battery preparation technology flow chart of the gradient-structure with composition change.
Fig. 6 is that, with different Cu, Zn, Hg, the cadmium telluride diaphragm solar battery of the gradient-structure of S doping concentrations prepares work
Skill flow.
Fig. 7 is the cadmium telluride diaphragm solar battery preparation technology stream of the gradient-structure changed with different grain sizes
Journey.
Embodiment
With reference to embodiment, the present invention is described further.
As in Figure 2-4, a kind of cadmium telluride diaphragm solar battery with gradient-structure, according to incident light direction, according to
It is secondary to be encapsulated including electrode, CdS Window layers, CdTe absorbed layers, back contact, metal back electrode, back reflection before glass substrate, TCO
Material and back-panel glass, wherein CdTe absorbed layers (p layers) and (i layers) formation pn-junctions of CdS Window layers.
CdTe absorbed layers in the pn-junction of the cadmium telluride diaphragm solar battery are CdxTeyGradient-structure, wherein 0≤x
≤ 1,0≤y≤1, the gradient-structure is the sandwich construction with Graded band-gap；The CdxTeyThe energy gap of gradient-structure exists
Between 1.6eV-1.3eV, from the first floor to last layer from high energy gap layer to low energy gap layer even transition, and between two layers of arbitrary neighborhood
Energy gap difference is between 0.01-0.1eV..
The CdxTeyThe gross thickness of gradient-structure is between 0.1 micron to 3 microns.The CdxTeyThe energy of gradient-structure
The form of even transition of the gap according to energy gap difference between 0.01-0.05eV.The CdxTeyEach transition zone in gradient-structure
Thickness be 1nm-10nm between.
One or more of the gradient-structure in following three kinds of forms：
(1) CdxTeyGradient-structure is by Cd miscellaneous Cu Erbium-dopedxTeyLayer even transition arrive by it is other so that energy gap reduction
Material doping CdxTeyLayer form, it is described it is other cause energy gap reduction materials in Zn, Hg, Se, Mg and S one
Plant or several；Wherein Cu atom doped amount is from 25% even transition to 0%, and the atom of other materials that energy gap is reduced is mixed
Miscellaneous amount is from 0% even transition to 25% (as shown in Figure 2), the shape of even transition of the energy gap according to energy gap difference between 0.01eV
Formula；
(2) CdxTeyGradient-structure gradually increases for Cd content, and the form that Te content is gradually decreased is (such as Fig. 3 institutes
Show), the form of even transition of the energy gap according to energy gap difference between 0.02eV；；
(3) CdxTeyGradient-structure is gradually increased to 1 micron of form, energy gap for CdTe crystallite dimension from 10nm
According to the form of even transition of the energy gap difference between 0.05eV；(as shown in Figure 4).
As shown in figure 5, the manufacture method of the cadmium telluride diaphragm solar battery with gradient-structure includes：
(1) glass substrate is cleaned；Glass substrate is existed with deionized water (DI) solution containing 1% soap first
60-80 DEG C carries out processing 5-20 minutes, is then further cleaned using ultrasonic wave and 60-80 DEG C of deionized water, and dry
It is dry.
(2) electrode before TCO is prepared on substrate；
Nesa coating SnO2：F layers are prepared by low-pressure chemical vapor phase deposition (LPCVD) method, and deposition gross pressure is
In 60torr, and underlayer temperature is 550 DEG C.Tetramethyl tin (TMT) is as the presoma of tin, and CBrF3 is the doping as F
Source.i-SnO2The thickness of thin layer of layer is 0.5-2 μm, and resistivity is about 1 ohmcm.Such as adopted using ITO as electrode before TCO
It is prepared by target and magnetically controlled sputter method with ITO.
(3) electrode to form sub- battery is split electrode before TCO using 355nm long wavelength lasers；
(4) glass substrate after scribing is cleaned again；
(5) in the glass substrate with conducting film, CdS film is prepared with chemical solution reaction method；
The raw material of cadmium uses 0.02-0.05 molar concentration cadmium acetates (CdAc2), the ammonium acetate of 0.5-2 molar concentration
(NH4Ac), the ammoniacal liquor (NH of 10-20 molar concentration4OH) and 0.05-0.1 molar concentration thiocarbamide (CS (NH3)2) it is used as sulphur
Source.Chemical solution reaction method depositing temperature is 80-95 DEG C, and CdS film deposit thickness is 80-200 nanometers.After the completion of plating mould, base
Plate and then taken out from bath, be put into warm deionized water, and with ultrasonically treated (about 2 minutes) to remove the CdS loosely adhered to
Particulate, then with dry N2Drying.
(6) preparation of cadmium telluride gradient-structure：
Cadmium telluride gradient-structure is prepared using co-evaporation method, first removes the CdS layer of substrate back before preparing with concentrated hydrochloric acid, then
Watery hydrochloric acid (wherein hydrochloric acid：Deionized water=1:40) solution is washed 3-5 seconds, is then cleaned and is dried with deionized water.Substrate is filled
It is loaded in behind settling chamber, under 400 DEG C and CO and CO2 or H2 of atmosphere, pre-processes 15 minutes.When after cooling to 200 DEG C, reative cell
Vacuum be extracted into 0.02 Torr of pressure, then pass to helium, when reaching 10-20 Torrs of pressure, start to plate buffer layer thin film, so
Metacoxal plate temperature is raised to as 600-650 DEG C, and CdTe and Zn, Hg and the miscellaneous CdTe graphite boats source temperatures of S Erbium-doped are 650-750
DEG C, prepared by 1100-1400 DEG C of Cu raw graphite boats source temperature carrys out cadmium telluride gradient-structure.
The cadmium telluride raw material of evaporation source is according to the miscellaneous Cd of Cu Erbium-doped in cadmium telluride gradient-structurexTey(1.4-1.6eV)/Cu,Zn,Hg
The miscellaneous Cd with S Erbium-dopedxTey(1.3-1.5eV) (1 >=x >=0,1 >=y >=0) is by changing Cu, Zn, the Hg and S miscellaneous amounts of Erbium-doped (miscellaneous amounts of Erbium-doped
From 0 to 25%), and x and y ratio are adjusted, and adjust grain size from 10nm to 1 μm to adjust cadmium telluride
The energy gap matching of material, by adjusting substrate temperature from 500 to 650 DEG C, Cu, Zn, CdTe graphite boat evaporation sources miscellaneous Hg and S Erbium-doped
Temperature is from 600 to 750 DEG C, and sedimentation rate controls the CdTe grain sizes to reach the adjustment of CdTe energy gaps.Often plate one
Tunic, any oxide loosely adhered to or CdTe particulates are removed with dry nitrogen.
(7)CdCl2Annealing
After CdTe gradient-structures deposition is completed, made annealing treatment using caddy.Not by the tellurium of annealing
The photoelectric conversion of cadmium solar cell is typically only between 6% and 10%, and the photoelectricity passed through after caddy makes annealing treatment
Conversion ratio can reach 12%-15%.Before annealing processing, CdTe gradient-structures are placed in the 75% of a saturation caddy
Methanol solution (saturated solution：500 ml methanols contain 7.5 grams of caddies).The substrate of CdTe gradient-structures is immersed at 50-70 DEG C
Bubble is after 15 minutes, the dry N2 dryings of taking-up.It is put into oven in 100sccm helium stream and 25sccm O2Under air-flow
With 360 DEG C -450 DEG C at a temperature of toast 40 minutes.It is cooled to after 50 DEG C, any excessive cadmium is removed with deionized water rinsing.
(8, using machinery and laser technology scribing film plating layer, are easy to metal back electrode as wire connexon battery；
(9) back-contact electrode is prepared
Using 88:1:35 phosphoric acid：Nitric acid：The solution of deionized water is cleaned and carved to the substrate of CdTe gradient-structures
Erosion, the total time of etching is about 30-60 seconds, forms the rich Te of cleaning surface.
4 grams of HgTe:Cu (Cu of about 2% atomic ratio), which is doped to row in 10g graphite powders, turns into graphite paste as back of the body electricity
Pole raw material.Back electrode is prepared with the method for mould printing, in oven in 100sccm helium stream, at 250-350 DEG C,
30 minutes, then the method for mould printing prepares and stamps a thin layer of silver paste, and toasted 1-2 hour in 100 DEG C of baking boxs.Also have
Metal back electrode is prepared using using magnetron sputtering；
(10) using machinery and laser technology scribing Cadimium telluride thin film and metal back electrode, single sub- battery is formed；
(11) laser scribing is carried out to battery edge；
(12) circuit connection and encapsulation are carried out to battery.
Claims (7)
1. a kind of preparation method of the cadmium telluride diaphragm solar battery with gradient-structure, cadmium telluride diaphragm solar battery bag
The pn-junction formed by CdTe absorbed layers and CdS Window layers is included, it is characterized in that, the pn-junction of the cadmium telluride diaphragm solar battery
In CdTe absorbed layers be CdxTeyGradient-structure, wherein 0≤x≤1,0≤y≤1, the gradient-structure is with Graded band-gap
Sandwich construction；The CdxTeyThe energy gap of gradient-structure between 1.6eV-1.3eV, from the first floor to last layer from high energy gap layer to
Energy gap difference between low energy gap layer even transition, and two layers of arbitrary neighborhood is between 0.01-0.1eV；It is characterized in that, it is described to have
The CdTe absorbed layers of gradient-structure are prepared using co-evaporation method, and concrete technology control parameter includes：First removed before preparing with concentrated hydrochloric acid
Go the CdS layer of substrate back, then dilute hydrochloric acid solution to wash 3-5 seconds, then cleaned and dried with deionized water；Substrate is loaded in heavy
Behind product room, at a temperature of 380 DEG C -420 DEG C, in CO, CO2Or H2Atmosphere under, pre-process 15-20 minutes；Be cooled to 150 DEG C-
At 200 DEG C, the vacuum of reative cell is extracted into 0.01-0.03 Torrs of pressure, then passes to helium, when reaching 10-20 Torrs of pressure,
Start to plate buffer layer thin film, then substrate temperature is raised to as 600 DEG C -650 DEG C, the CdTe graphite boats that CdTe and Zn, Hg, S adulterate
Source temperature is 650 DEG C -750 DEG C, and prepared by 1100 DEG C -1400 DEG C of Cu raw graphite boats source temperature carrys out cadmium telluride gradient knot
Structure, has often plated a tunic, and the oxide or CdTe particulates loosely adhered to is removed with dry nitrogen.
2. there is the preparation method of the cadmium telluride diaphragm solar battery of gradient-structure according to claim 1, it is characterized in that,
The CdxTeyOne or more of the gradient-structure in following three kinds of forms：
(1) CdxTeyGradient-structure is the Cd adulterated by CuxTeyLayer even transition is to by other materials for causing energy gap to reduce
The Cd of dopingxTeyThe form of layer, described other one kind or several for causing the material of energy gap reduction in Zn, Hg, Se, Mg and S
Kind；Wherein Cu atom doped amount from 25% even transition to 0%, the atom doped amounts of other materials for causing energy gap reduction from
0% even transition is to 25%；
(2) CdxTeyGradient-structure gradually increases for Cd content, the form that Te content is gradually decreased；
(3) CdxTeyGradient-structure is gradually increased to 3 microns of form for CdTe crystallite dimension from 10nm.
3. the preparation method of the cadmium telluride diaphragm solar battery according to claim 1 or claim 2 with gradient-structure, its feature
It is, the CdxTeyThe gross thickness of gradient-structure is between 0.1 micron to 3 microns.
4. the preparation method of the cadmium telluride diaphragm solar battery according to claim 1 or claim 2 with gradient-structure, its feature
It is, the CdxTeyThe form of uniform reduction of the energy gap of gradient-structure according to energy gap difference between 0.01-0.05eV.
5. the preparation method of the cadmium telluride diaphragm solar battery according to claim 1 or claim 2 with gradient-structure, its feature
It is, the CdxTeyThe thickness of each transition zone is between 1nm-100nm in gradient-structure.
6. there is the preparation method of the cadmium telluride diaphragm solar battery of gradient-structure according to claim 5, it is characterized in that,
The CdxTeyThe thickness of each transition zone is between 1nm-10nm in gradient-structure.
7. there is the preparation method of the cadmium telluride diaphragm solar battery of gradient-structure according to claim 1, it is characterized in that,
After CdTe gradient-structures deposition is completed, made annealing treatment using caddy：CdTe gradient-structures are placed in a saturation chlorine
In the 60%-80% methanol solutions of cadmium；The substrate of CdTe gradient-structures takes out and used after 50 DEG C -70 DEG C are soaked 15 minutes
Dry N2Drying, is put into oven in 100sccm helium stream and 25sccm O2Temperature under air-flow with 360 DEG C -450 DEG C
Degree lower baking 40-45 minutes, is cooled to after 45 DEG C -50 DEG C, is rinsed with deionized water and remove excessive cadmium.
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| CN104810424A (en) * | 2015-04-17 | 2015-07-29 | 四川大学 | CdTe thin film solar battery with CdxTe insertion layer |
| CN105355699B (en) * | 2015-11-04 | 2017-07-11 | 湖南共创光伏科技有限公司 | A kind of many many lamination cadmium telluride diaphragm solar batteries of knot and preparation method thereof |
| CN106356417B (en) * | 2016-11-25 | 2018-11-13 | 中国科学院电工研究所 | A kind of CIGS/CdTe Gradient Absorptions layer film solar cell and preparation method thereof |
| CN106449810B (en) * | 2016-11-25 | 2017-11-14 | 中国科学院电工研究所 | A kind of CdTe/CIGS Gradient Absorptions layer film solar cell and preparation method thereof |
| CN107910394A (en) * | 2017-11-06 | 2018-04-13 | 成都中建材光电材料有限公司 | A kind of absorbed layer of cadmium telluride diaphragm solar battery mixes selenium technique |
| CN110176503A (en) * | 2019-06-05 | 2019-08-27 | 浙江力晟玻璃科技有限公司 | A kind of cadmium telluride power generating glass |
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