CN102074590A - Back contact electrode in cadmium telluride membrane solar cell structure and preparation method thereof - Google Patents
Back contact electrode in cadmium telluride membrane solar cell structure and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a back contact electrode in a CdTe membrane solar cell structure. The electrode comprises a transparent conductive glass layer, a window layer, a light absorbing layer and a blocking layer and is characterized in that: a graphene membrane layer serving as the back contact electrode is prepared on the back face of an anti-insertion layer; and the thickness of the graphene layer is between 0.1 mu m and 1 millimeter. A preparation method of the back contact electrode comprises preparation of the transparent conductive glass layer, preparation of the window layer, preparation of the light absorbing layer and preparation of the blocking layer and is characterized by comprising the following steps of: adding an adhesive into graphene so as to prepare graphene slurry; and preparing the graphene slurry into a graphene layer. The back contact electrode and the preparation method have the advantages that: a process adopted by the preparation method is compatible with the conventional CdTe cell process, and a new measure for realizing a low-cost, high-performance and large-scale CdTe cell is provided.
Description
Technical field
The present invention relates to back-contact electrode and preparation method in a kind of cadmium telluride diaphragm solar battery structure, relate to a kind of Graphene or rather and be applied to cadmium telluride battery contact back electrode and preparation method, belong to microelectronics technology.
Background technology
Enter 21st century the mankind, environmental pollution and energy shortage are more and more restricting the sustainable development of society, renewable energy technologies such as solar energy have been represented the developing direction of clean energy resource, to enter human energy resource structure and become the important component part of basic energy resource as the solar energy power generating of tool sustainable development desired characteristics, China is also listed its important foundation condition as the novel society that makes up harmonious sustainable development in the national medium-term and long-term science and technology development planning in.From wide significance, the tellurian energy all comes from the sun after all.The energy under nuclear energy and geothermal energy etc. can be thought to store in earth forming process, other all energy all come from the huge energy that thermonuclear reaction discharged that the sun takes place, and comprise regenerative resource and fossil energy.The total radiation energy that the sun is launched is approximately 3.75 * 10
26W considers after the reflection and absorption of earth atmosphere that the solar energy that earth surface is accepted in 1 year is up to 1.05 * 10
18KWh approximately is 10,000 times of beginning of this century whole world primary energy total amount consumed.The sun has brought light to the mankind, has also brought inexhaustible, nexhaustible natural energy resources to the mankind, makes us see following hope.
But the CdTe solar cell is the thin film solar cell of efficient, the low-cost large-scale industrial production of a new generation, is described as one of the most promising solar cell.The thickness of CdTe solar cell absorbed layer is 1% of current commercial silicon solar cell only, and materials are considerably less, and cost is very low; And its photoelectric conversion efficiency is high relatively in the thin film type solar battery.U.S. NREL National Laboratory has the world record of such battery, under the simulated solar illumination of AM1.5, has 16.5% photoelectric conversion efficiency, though apart from theoretical efficiency 28% very big space is arranged still.CdTe has the advantage of the following aspects inherence as the photoelectric conversion material of solar cell:
(1) CdTe is an II-VI compound semiconductor, and energy gap is 1.45eV, so it is in optimal solar energy wave band place to the response of spectrum.The absorption coefficient of CdTe at visible-range up to 10
5Cm
-1, 99% photon can be absorbed in the absorbed layer of 1-2 micron thickness, and therefore, with this material preparation solar cell, desired thickness is about 2 microns in theory, and material consumption is few.
(2) the CdTe battery is compared with other compound battery, as comparing with CIGS (Copper Indium Gallium Selenide) compound battery, its biggest advantage of CdTe battery is that phasor is extremely simple, can be easy to prepare single-phase CdTe crystal film, can prepare with multiple method for manufacturing thin film.And the CIGS battery has kind more than 20 to exist mutually, therefore to preparing single chalcopyrite phase, has proposed stern challenge, and it requires technologies such as accurately harsh online detection and subsequent heat treatment, and this has directly caused this battery large-scale production to be made slow progress.The present laboratory conversion peak efficiency of CdTe is 16.5%, is only second to CIGS battery conversion efficiency (20.3%).And CdTe material phasor is extremely simple, and preparation window broad makes the production of CdTe large-scale commercial applications succeed.
(3) CdTe does not have photic attenuating effect, and illumination can improve the conversion efficiency of solar cell, so the long working life of such solar cell.Existing result shows that the life-span of CdTe battery is longer than monocrystalline silicon battery (being about 40 years).The CdTe solar cell is difficult to be equal at all many other solar cells in aspect such as temperature stability, chemical stability, capability of resistance to radiation, low light level performances, is desirable space power system.
Graphene (graphene) is that what to be made of carbon atom is the monoatomic layer material with bi-dimensional cellular shape structure of elementary cell with the phenyl ring.It can warpage becomes the fullerene (fullerene) of zero dimension (0D), be rolled into the carbon nano-tube (carbon nanotube/CNT) of one dimension (1D) or be stacked to the graphite (graphite) of three-dimensional (3D), so Graphene is the elementary cell that constitutes other graphite materials.Why Graphene can cause rapidly that countries in the world scientist's extensive attention is because it has not only contained abundant and novel physical phenomenon, having important theoretical research is worth, and its particular structure and excellent performance might make it obtain great practical application in every field, for economy, the social development in future provides new strong growth point.The most peculiar part of Graphene is that it has unique electronic structure and electrical properties.Valence band of Graphene (pi-electron) and conduction band (π
*Electronics) intersecting at Fermi level place (K and K ' point), is that energy gap is zero semiconductor, and its charge carrier presents linear dispersion relation near Fermi level.And electronic motion speed reaches 1/300 of the light velocity in the Graphene, and its electronic behavior need be described with the Dirac equation in the relativistic quantum mechanics, and the effective mass of electronics is zero.Therefore, Graphene becomes the model system that unique description in the condensed state physics does not have quality dirac fermion (massless Dirac fermions) so far, and this phenomenon has caused the electrical properties of many novelties.For example, Graphene has 10 times of high carrier mobilities to commercial silicon chip and (reaches 15000cm
2V
-1s
-1), and charge carrier shows the ballistic transport characteristic of tangible ambipolar field performance characteristic and room temperature submicron-scale, and high and continuously adjustable carrier concentration (can reach 10
13Cm
-2); The intensity of Graphene can reach 130GPa, is more than 100 times of steel.The work function of Graphene can be suitable as the contact electrode of p type greater than 5eV, and these are characterized as Graphene and are applied to the CdTe back electrode and lay a good foundation.
The work function of CdTe is about 5.5eV, and so high work function makes CdTe have a schottky junction with existing as not forming ohmic contact between the material of back electrode, and the existence of this knot has a strong impact on charge carrier and conducts.The metal that is used for the CdTe back electrode now is generally the noble metal of high work function, can adopt under the situation of laboratory research, if be applied to the cost that industrial production must consider that it is expensive.The application intends adopting high work function, high conductivity and cheaply Graphene as the back-contact electrode of CdTe battery to overcome the deficiencies in the prior art.
Summary of the invention
The object of the present invention is to provide back-contact electrode and preparation method in a kind of cadmium telluride (CdTe) film solar battery structure, utilization of the present invention can reach 10
13Cm
-2High and continuously adjustable carrier concentration adopts low cost to smear or printing technology, preparation CdTe battery back electrode.
1. the structure (as Fig. 1) of the CdTe thin-film solar cells of the present invention's proposition is by conductive glass layer | resistive formation | and Window layer | light-absorption layer | the barrier layer | Graphene back-contact electrode battery structure, it is characterized in that,
1) conductive glass layer
Conducting Glass is tin-doped indium oxide (AZO), Al-Doped ZnO or fluorine doped tin oxide glass.Thickness 1mm～the 3mm of glass substrate, above the thickness of conductive layer be 300nm～3 μ m.
2) resistive formation
Resistive formation is an indium oxide, aluminium oxide or tin oxide, zinc oxide; Thickness is 20～100nm.Also can select without resistive formation.
3) window (cadmium sulfide layer)
Cadmium sulfide layer, thickness are 20nm～300 μ m.
4) light-absorption layer (cadmium-telluride layer)
Thickness is at 600nm～10 μ m.
5) barrier layer
Zinc telluridse/mix copper zinc telluridse composite bed, its thickness is at 5nm～500nm.This layer also can be with tellurium mercury/mix copper tellurium mercury composite bed, and thickness is 5nm～500nm.
6) Graphene back-contact electrode
The present invention relates to Graphene, can obtain by the mode that market is bought and oneself prepares.In Graphene, add adhesive and prepare the Graphene slurry, be prepared into the graphene film layer by the Graphene slurry then,
1) solute of employing Kynoar (PVDF), 1-Methyl-2-Pyrrolidone (NMP) is a solvent, presses 0.01g/ml to 1g/ml proportional arrangement adhesive.
2) with 1) mixed liquor mix through stirring fully.
3) Graphene is inserted 2) adhesive in, the addition of Graphene be 0.01g/ml to 100g/ml, through fully stirring, obtains thick Graphene and starches.
4) with the Graphene for preparing, obtain the graphene film layer by printing, spin coating or czochralski method at the back side, CdTe battery barrier layer, can be used as battery contact back electrode.The thickness of back-contact electrode is 0.1 μ m～1mm.
5) according to need, in the Graphene slurry of step 3 preparation by 1%～40%wt ratio (is benchmark with the Graphene slurry) with the Cu powder or mix copper tellurium mercury powder and sneak into Graphene slurry, fully stirring.
2. the present invention includes growth, burn into annealing in process and printing, the spin coating of each each function film of battery and lift the preparation graphene film, be characterised in that:
1) conductive layer preparation on the clear glass: first ultrasonic glass cleaning substrate, earlier with carbon tetrachloride (perhaps cleaning agent or omit this step), then pass through according to this acetone, absolute ethyl alcohol,, washed with de-ionized water at last, nitrogen dries up; Depositing conducting layer then;
2) resistive formation preparation: adopt physical sputtering method (sputter), vapour deposition method or CVD legal system are equipped with resistive formation; Can select without resistive formation;
3) Window layer preparation: adopt chemical bath deposition (CBD), physical sputtering method (sputter), vapour deposition method or CVD legal system are equipped with the CdS layer;
4) light-absorption layer preparation: adopt nearly vacuum sublimation, electrochemical deposition, physical sputtering or CVD legal system to be equipped with the CdTe layer;
5) extinction district heat treatment: adopt caddy to be applied in the CdTe flash annealing, perhaps at CdCl
2Anneal under the atmosphere;
6) barrier layer preparation: adopt sputter, evaporation or CVD legal system to be equipped with zinc telluridse and mix copper zinc telluridse composite bed or tellurium mercury and mix copper tellurium mercury composite bed, under nitrogen or hydrogen atmosphere, anneal; Can select without the barrier layer.
7) back electrode preparation: adopt printing, spin coating and the mode that lifts to prepare the battery back of the body and contact Graphene electrodes.If at the transparent conducting glass conductive layer, in the Graphene pulp preparation, need mixed C u or HgTe:Cu powder.
Description of drawings
The structural representation of Fig. 1 CdTe battery;
The electro-conductive glass of Fig. 2 preparation;
The SEM photo of the cadmium sulphide membrane of Fig. 3 preparation;
The Graphene back electrode of Fig. 4 preparation; A) 2,000 *; B) 10,000 *
Fig. 5 cadmium telluride battery (Graphene back electrode) transformation efficiency, (a) printing Graphene back electrode; (b) spin coating Graphene back electrode; (c) lift the Graphene back electrode.
Embodiment
Introduce embodiments of the invention below, with further increase to understanding of the present invention, with reference to CdTe solar cell schematic diagram, accompanying drawing 1, contrast accompanying drawing 2, accompanying drawing 3 and accompanying drawing 4 describe preparation method of the present invention and optimal way thereof in detail, and embodiment the results are shown in accompanying drawing 5.But the present invention is limited to embodiment absolutely not.
Embodiment 1:
Transparency conducting layer preparation: adopt sputtering method to prepare the AZO electro-conductive glass, the glass substrate temperature is 600 ℃ of room temperatures, carrier gas is argon gas or argon hydrogen gaseous mixture (wherein hydrogen is less than 10%), reaction pressure is 0.1Pa, gas flow 5sccm (standard cubic centimeter per minute, standard cubic centimeters per minute), power is 50W, range is 5cm, wherein N
2As carrier gas.Deposit thickness is about 600nm.Obtain transparent conducting glass (Fig. 2) with conductive layer.
The Window layer preparation: adopt the sputtering method preparation, the Conducting Glass temperature is a room temperature, and reaction pressure is 0.1Pa, and power is 100W, and target is CdS target, wherein N
2As carrier gas, gas flow 5sccm.Deposit thickness is about 100nm (Fig. 3).
The light-absorption layer preparation: adopt the sputtering method preparation, above-mentioned underlayer temperature is 300 ℃, and reaction pressure is 0.1Pa, and power is 100W, and argon gas or argon oxygen gas mixture are as carrier gas, and gas flow 5sccm, target are the CdTe target, and deposit thickness is about 5～7 μ m.Material object is seen accompanying drawing 2
Barrier layer preparation: adopt sputtering method to prepare the ZnTe/ZnTe:Cu composite bed, above-mentioned underlayer temperature is 300 ℃, reaction pressure is 0.1Pa, power is 100W, argon gas or argon oxygen gas mixture are as carrier gas, gas flow 5sccm, target are ZnTe target and ZnTe:Cu, and deposit thickness is respectively 20nm and 70nm.
The back-contact electrode preparation: pour Kynoar (PVDF) solvent into container, adopt magnetic agitation, be heated to 80 ℃, adding 1-Methyl-2-Pyrrolidone (NMP) solvent is adhesive, the about 20g/L of concentration.Mix through stirring fully.Average mark adds Graphene four times, and each 28-32 minute at interval, fully stir, obtain thick Graphene slurry.Battery is placed on the printing machine, fixing.After graphite slurry fully stirs, be poured on the printing screen plate, adopt mode of printing to prepare the battery back electrode.Place 150 ° of c oven for drying, finish battery unit structure.The photo of the Graphene back-contact electrode of preparation is as Fig. 4 (a) with (b), and its transformation efficiency is shown in Fig. 5 (a), and transformation efficiency is 7.41%.
Embodiment 2:
The transparency conducting layer preparation: adopt LPCVD deposition FTO electro-conductive glass, underlayer temperature is 400 ℃, and reaction pressure is 3kPa, and the reaction precursor body is Tetramethyltin (TMT), and Bromotrifluoromethane (CBrF3) gas provides F the source, feeds O simultaneously
2And N
2, N wherein
2As carrier gas.Deposit thickness is about 500nm.
The Window layer preparation: adopt the sputtering method preparation, the Conducting Glass temperature is a room temperature, and reaction pressure is 0.1Pa, and power is 100W, and target is CdS target, wherein N
2As carrier gas, gas flow 5sccm.Deposit thickness is about 100nm.。
The light-absorption layer preparation: adopt the sputtering method preparation, above-mentioned underlayer temperature is 300 ℃, and reaction pressure is 0.1Pa, and power is 100W, and argon gas or argon oxygen gas mixture are as carrier gas, and gas flow 5sccm, target are the CdTe target, and deposit thickness is about 5～7 μ m.
The barrier layer preparation: adopt sputtering method to prepare ZnTe and ZnTe:Cu composite bed, underlayer temperature is 300 ℃, and reaction pressure is 0.1Pa, power is 100W, and argon gas or argon oxygen gas mixture be as carrier gas, gas flow 5sccm, target is ZnTe target and ZnTe:Cu, and deposit thickness is respectively 20nm and 70nm.
The back-contact electrode preparation: pour Kynoar (PVDF) solvent into container, adopt magnetic agitation, be heated to 80 ℃, adding 1-Methyl-2-Pyrrolidone (NMP) solvent is adhesive, the about 20g/L of concentration.Mix through stirring fully.Average mark adds Graphene four times, and each 28-32 minute at interval, fully stir, obtain thick Graphene slurry.Battery is placed on the printing machine, fixing.After graphite slurry fully stirs, be poured on the printing screen plate, adopt mode of printing to prepare the battery back electrode.Place 150 ° of c oven for drying, finish battery unit structure.
All the other are with embodiment 1.
Embodiment 3:
The transparency conducting layer preparation: adopt LPCVD deposition FTO electro-conductive glass, underlayer temperature is 400 ℃, and reaction pressure is 3kPa, and the reaction precursor body is Tetramethyltin (TMT), and Bromotrifluoromethane (CBrF3) gas provides F the source, feeds O simultaneously
2And N
2, N wherein
2As carrier gas.Deposit thickness is about 500nm.
The Window layer preparation: adopt the chemical bath legal system to be equipped with the CdS layer, reactant is ammonium acetate, cadmium acetate, ammoniacal liquor and thiocarbamide.At first will add deionized water in the airtight container, be heated to 80 ℃, add cadmium acetate, ammonium acetate, ammoniacal liquor, deposit thickness is about 100nm.
The light-absorption layer preparation: adopt the sputtering method preparation, above-mentioned underlayer temperature is 300 ℃, and reaction pressure is 0.1Pa, and power is 100W, and argon gas or argon oxygen gas mixture are as carrier gas, and gas flow 5sccm, target are the CdTe target, and deposit thickness is about 5～7 μ m.
Barrier layer preparation: adopt sputtering method to prepare the ZnTe/ZnTe:Cu composite bed, above-mentioned underlayer temperature is 300 ℃, reaction pressure is 0.1Pa, power is 100W, argon gas or argon oxygen gas mixture are as carrier gas, gas flow 5sccm, target are ZnTe target and ZnTe:Cu, and deposit thickness is respectively 20nm and 70nm.
The back-contact electrode preparation: pour Kynoar (PVDF) solvent into container, adopt magnetic agitation, be heated to 80 ℃, adding 1-Methyl-2-Pyrrolidone (NMP) solvent is adhesive, the about 20g/L of concentration.Mix through stirring fully.The siccative average mark adds Graphene four times, and each 28-32 minute at interval, fully stir, obtain thick Graphene slurry.Battery is placed on the printing machine, fixing.After graphite slurry fully stirs, be poured on the printing screen plate, adopt mode of printing to prepare the battery back electrode.Place 150 ° of c oven for drying, finish battery unit structure.All the other are with embodiment 1.
Embodiment 4
The transparency conducting layer preparation: adopt LPCVD deposition FTO electro-conductive glass, underlayer temperature is 400 ℃, and reaction pressure is 3kPa, and the reaction precursor body is Tetramethyltin (TMT), and Bromotrifluoromethane (CBrF3) gas provides F the source, feeds O simultaneously
2And N
2, N wherein
2As carrier gas.Deposit thickness is about 500nm.
The Window layer preparation: adopt the chemical bath legal system to be equipped with the CdS layer, reactant is ammonium acetate, cadmium acetate, ammoniacal liquor and thiocarbamide.At first will add deionized water in the airtight container, be heated to 80 ℃, add cadmium acetate, ammonium acetate, ammoniacal liquor, deposit thickness is about 100nm.
The light-absorption layer preparation: nearly vacuum sublimation legal system is equipped with the CdTe film, and underlayer temperature is 500 ℃, and argon gas or argon oxygen gas mixture are as carrier gas, and reaction pressure 1kPa, evaporation source are CdTe, and deposit thickness is about 7 μ m.
Barrier layer preparation: adopt sputtering method to prepare the ZnTe/ZnTe:Cu composite bed, above-mentioned underlayer temperature is 300 ℃, reaction pressure is 0.1Pa, power is 100W, argon gas or argon oxygen gas mixture are as carrier gas, gas flow 5sccm, target are ZnTe target and ZnTe:Cu, and deposit thickness is respectively 20nm and 70nm.
The back-contact electrode preparation: pour Kynoar (PVDF) solute into container, adopt magnetic agitation, be heated to 80 ℃, adding 1-Methyl-2-Pyrrolidone (NMP) solvent is adhesive, the about 20g/L of concentration.Mix through stirring fully.Average mark adds Graphene four times, and each 28-32 minute at interval, fully stir, obtain thick Graphene slurry.Battery is placed on the printing machine, fixing.After the Graphene slurry fully stirs, be poured on the printing screen plate, adopt mode of printing to prepare the battery back electrode.Place 150 ° of c oven for drying, finish battery unit structure.All the other are with embodiment 1.
Embodiment 5
The transparency conducting layer preparation: adopt LPCVD deposition FTO electro-conductive glass, underlayer temperature is 400 ℃, and reaction pressure is 3kPa, and the reaction precursor body is Tetramethyltin (TMT), and Bromotrifluoromethane (CBrF3) gas provides F the source, feeds O simultaneously
2And N
2, N wherein
2As carrier gas.Deposit thickness is about 500nm.
The Window layer preparation: adopt the chemical bath legal system to be equipped with the CdS layer, reactant is ammonium acetate, cadmium acetate, ammoniacal liquor and thiocarbamide.At first will add deionized water in the airtight container, be heated to 80 ℃, add cadmium acetate, ammonium acetate, ammoniacal liquor, deposit thickness is about 100nm.
The light-absorption layer preparation: nearly vacuum sublimation legal system is equipped with the CdTe film, and underlayer temperature is 500 ℃, and argon gas or argon oxygen gas mixture are as carrier gas, and reaction pressure 1kPa, evaporation source are CdTe, and deposit thickness is about 7 μ m.
The back-contact electrode preparation: pour Kynoar (PVDF) solvent into container, adopt magnetic agitation, be heated to 80 ℃, adding 1-Methyl-2-Pyrrolidone (NMP) solvent is adhesive, the about 20g/L of concentration.Mix through stirring fully.The siccative average mark adds Graphene four times, and each 28-32 minute at interval, fully stir, obtain thick Graphene slurry.The Cu powder that mixes 6%wt fully stirs.Battery is placed on the printing machine, fixing.After graphite slurry fully stirs, be poured on the printing screen plate, adopt mode of printing to prepare the battery back electrode.Place 150 ℃ of oven for drying, finish battery unit structure.All the other are with embodiment 1.
Embodiment 6
The transparency conducting layer preparation: adopt LPCVD deposition FTO electro-conductive glass, underlayer temperature is 400 ℃, and reaction pressure is 3kPa, and the reaction precursor body is Tetramethyltin (TMT), and Bromotrifluoromethane (CBrF3) gas provides F the source, feeds O simultaneously
2And N
2, N wherein
2As carrier gas.Deposit thickness is about 500nm.
The Window layer preparation: adopt the chemical bath legal system to be equipped with the CdS layer, reactant is ammonium acetate, cadmium acetate, ammoniacal liquor and thiocarbamide.At first will add deionized water in the airtight container, be heated to 80 ℃, add cadmium acetate, ammonium acetate, ammoniacal liquor, deposit thickness is about 100nm.
The light-absorption layer preparation: nearly vacuum sublimation legal system is equipped with the CdTe film, and underlayer temperature is 500 ℃, and argon gas or argon oxygen gas mixture are as carrier gas, and reaction pressure 1kPa, evaporation source are CdTe, and deposit thickness is about 7 μ m.
Barrier layer preparation: adopt sputtering method to prepare the ZnTe/ZnTe:Cu composite bed, above-mentioned underlayer temperature is 300 ℃, reaction pressure is 0.1Pa, power is 100W, argon gas or argon oxygen gas mixture are as carrier gas, gas flow 5sccm, target are ZnTe target and ZnTe:Cu, and deposit thickness is respectively 20nm and 70nm.
The back-contact electrode preparation: pour Kynoar (PVDF) solvent into container, adopt magnetic agitation, be heated to 80 ℃, adding 1-Methyl-2-Pyrrolidone (NMP) solvent is adhesive, the about 20g/L of concentration.Mix through stirring fully.Average mark adds Graphene four times, and each 28-32 minute at interval, fully stir, obtain thick Graphene slurry, battery is placed on the spin coater, vacuum suction is fixed.After the Graphene slurry fully stirred, be poured on cell backside, the employing rotation parameter is 1000rpm/5s; 2000rpm/30s two step spin coatings prepare the battery back electrode.Place 150 ℃ of oven for drying, finish battery unit structure.Transformation efficiency is shown in Fig. 5 (b), and transformation efficiency reaches 6.5%.All the other are with embodiment 1.
Embodiment 7
The transparency conducting layer preparation: adopt LPCVD deposition FTO electro-conductive glass, underlayer temperature is 400 ℃, and reaction pressure is 3kPa, and the reaction precursor body is Tetramethyltin (TMT), and Bromotrifluoromethane (CBrF3) gas provides F the source, feeds O simultaneously
2And N
2, N wherein
2As carrier gas.Deposit thickness is about 500nm.
The Window layer preparation: adopt the chemical bath legal system to be equipped with the CdS layer, reactant is ammonium acetate, cadmium acetate, ammoniacal liquor and thiocarbamide.At first will add deionized water in the airtight container, be heated to 80 ℃, add cadmium acetate, ammonium acetate, ammoniacal liquor, deposit thickness is about 100nm.
The light-absorption layer preparation: nearly vacuum sublimation legal system is equipped with the CdTe film, and underlayer temperature is 500 ℃, and argon gas or argon oxygen gas mixture are as carrier gas, and reaction pressure 1kPa, evaporation source are CdTe, and deposit thickness is about 7 μ m.
The back-contact electrode preparation: pour Kynoar (PVDF) solvent into container, adopt magnetic agitation, be heated to 80 ℃, adding 1-Methyl-2-Pyrrolidone (NMP) solvent is adhesive, the about 20g/L of concentration.Mix through stirring fully.The siccative average mark adds Graphene four times, and each 28-32 minute at interval, fully stir, obtain thick Graphene slurry.The Cu powder that mixes 6%wt fully stirs.Battery is placed on the spin coater, and vacuum suction is fixed.After graphite slurry fully stirred, be poured on cell backside, the employing rotation parameter is 1000rpm/5s; 2000rpm/30s two step spin coatings prepare the battery back electrode.Place 150 ° of c oven for drying, finish battery unit structure.Transformation efficiency shown in Fig. 5 (b), transformation efficiency be 6.5% all the other with embodiment 1.
Embodiment 8
The transparency conducting layer preparation: adopt LPCVD deposition FTO electro-conductive glass, underlayer temperature is 400 ℃, and reaction pressure is 3kPa, and the reaction precursor body is Tetramethyltin (TMT), and Bromotrifluoromethane (CBrF3) gas provides F the source, feeds O simultaneously
2And N
2, N wherein
2As carrier gas.Deposit thickness is about 500nm.
The Window layer preparation: adopt the chemical bath legal system to be equipped with the CdS layer, reactant is ammonium acetate, cadmium acetate, ammoniacal liquor and thiocarbamide.At first will add deionized water in the airtight container, be heated to 80 ℃, add cadmium acetate, ammonium acetate, ammoniacal liquor, deposit thickness is about 100nm.
The light-absorption layer preparation: nearly vacuum sublimation legal system is equipped with the CdTe film, and underlayer temperature is 500 ℃, and argon gas or argon oxygen gas mixture are as carrier gas, and reaction pressure 1kPa, evaporation source are CdTe, and deposit thickness is about 7 μ m.
Barrier layer preparation: adopt sputtering method to prepare the ZnTe/ZnTe:Cu composite bed, above-mentioned underlayer temperature is 300 ℃, reaction pressure is 0.1Pa, power is 100W, argon gas or argon oxygen gas mixture are as carrier gas, gas flow 5sccm, target are ZnTe target and ZnTe:Cu, and deposit thickness is respectively 20nm and 70nm.
The back-contact electrode preparation: pour Kynoar (PVDF) solvent into container, adopt magnetic agitation, be heated to 80 ℃, adding 1-Methyl-2-Pyrrolidone (NMP) solvent is adhesive, the about 20g/L of concentration.Mix through stirring fully.The siccative average mark adds Graphene four times, and each 28-32 minute at interval, fully stir, obtain thick Graphene slurry.After the Graphene slurry fully stirred, battery front side is pasted blue film protection, immerse in the Graphene slurry, lift, take off and be placed on 150 ° of c oven for drying, peel off positive blue film, finish battery unit structure with 2mm/s speed.Transformation efficiency is shown in Fig. 5 (c), and transformation efficiency is 7.86%.All the other are with embodiment 1.
Embodiment 9
The preparation of transparent conducting glass layer: adopt LPCVD deposition FTO electro-conductive glass, underlayer temperature is 400 ℃, and reaction pressure is 3kPa, and the reaction precursor body is Tetramethyltin (TMT), and Bromotrifluoromethane (CBrF3) gas provides F the source, feeds O simultaneously
2And N
2, N wherein
2As carrier gas.Deposit thickness is about 500nm.
The Window layer preparation: adopt the chemical bath legal system to be equipped with the CdS layer, reactant is ammonium acetate, cadmium acetate, ammoniacal liquor and thiocarbamide.At first will add deionized water in the airtight container, be heated to 80 ℃, add cadmium acetate, ammonium acetate, ammoniacal liquor, deposit thickness is about 100nm.
The light-absorption layer preparation: nearly vacuum sublimation legal system is equipped with the CdTe film, and underlayer temperature is 500 ℃, and argon gas or argon oxygen gas mixture are as carrier gas, and reaction pressure 1kPa, evaporation source are CdTe, and deposit thickness is about 7 μ m.
Barrier layer preparation: adopt sputtering method to prepare the ZnTe/ZnTe:Cu composite bed, above-mentioned underlayer temperature is 300 ℃, reaction pressure is 0.1Pa, power is 100W, argon gas or argon oxygen gas mixture are as carrier gas, gas flow 5sccm, target are ZnTe target and ZnTe:Cu, and deposit thickness is respectively 20nm and 70nm.
The back-contact electrode preparation: pour Kynoar (PVDF) solvent into container, adopt magnetic agitation, be heated to 80 ℃, adding 1-Methyl-2-Pyrrolidone (NMP) solvent is adhesive, the about 20g/L of concentration.Mix through stirring fully.The Cu powder that mixes 6%wt fully stirs.The siccative average mark adds Graphene four times, and each 28-32 minute at interval, fully stir, obtain thick Graphene slurry.After graphite slurry fully stirred, battery front side is pasted blue film protection, immerse in the Graphene slurry, lift, take off and be placed on 150 ° of c oven for drying, peel off positive blue film, finish battery unit structure with 2mm/s speed.Transformation efficiency is 7.86% (shown in Fig. 5 (c)), and all the other are with embodiment 1.
Embodiment 10
The transparency conducting layer preparation: adopt LPCVD deposition FTO electro-conductive glass, underlayer temperature is 400 ℃, and reaction pressure is 3kPa, and the reaction precursor body is Tetramethyltin (TMT), and Bromotrifluoromethane (CBrF3) gas provides F the source, feeds O simultaneously
2And N
2, N wherein
2As carrier gas.Deposit thickness is about 500nm.
The resistive formation preparation: adopt LPCVD deposition SnO layer, reacting gas is 0.25sccmTetramethyltin (TMT), and 18sccmO2 and 15sccmN2, underlayer temperature are 550 ℃, and reaction pressure is 2kPa, and deposit thickness is 500nm
The Window layer preparation: adopt the chemical bath legal system to be equipped with the CdS layer, reactant is ammonium acetate, cadmium acetate, ammoniacal liquor and thiocarbamide.At first will add deionized water in the airtight container, be heated to 80 ℃, add cadmium acetate, ammonium acetate, ammoniacal liquor, deposit thickness is about 100nm.
The light-absorption layer preparation: nearly vacuum sublimation legal system is equipped with the CdTe film, and underlayer temperature is 500 ℃, and argon gas or argon oxygen gas mixture are as carrier gas, and reaction pressure 1kPa, evaporation source are CdTe, and deposit thickness is about 7 μ m.
The back-contact electrode preparation: pour Kynoar (PVDF) solvent into container, adopt magnetic agitation, be heated to 80 ℃, adding 1-Methyl-2-Pyrrolidone (NMP) solvent is adhesive, the about 20g/L of concentration.Mix through stirring fully.The Cu powder that mixes 6%wt fully stirs.The siccative average mark adds Graphene four times, and each 28-32 minute at interval, fully stir, obtain thick Graphene slurry.The Cu powder that mixes 6%wt fully stirs.After will mixing copper Graphene slurry and fully stirring, battery front side is pasted blue film protection, immerse graphite slurry, lift, take off and be placed on 150 ° of c oven for drying, peel off positive blue film, finish battery unit structure with 2mm/s speed.Transformation efficiency is 7.86% (shown in Fig. 5 (c)), and all the other are with embodiment 1.
Embodiment 11
The transparency conducting layer preparation: adopt LPCVD deposition FTO electro-conductive glass, underlayer temperature is 400 ℃, and reaction pressure is 3kPa, and the reaction precursor body is Tetramethyltin (TMT), and Bromotrifluoromethane (CBrF3) gas provides F the source, feeds O simultaneously
2And N
2, N wherein
2As carrier gas.Deposit thickness is about 500nm.
The resistive formation preparation: adopt LPCVD deposition SnO layer, reacting gas is 0.25sccmTetramethyltin (TMT), 18sccmO
2And 15sccmN
2, underlayer temperature is 550 ℃, and reaction pressure is 2kPa, and deposit thickness is 500nm
The Window layer preparation: adopt the chemical bath legal system to be equipped with the CdS layer, reactant is ammonium acetate, cadmium acetate, ammoniacal liquor and thiocarbamide.At first will add deionized water in the airtight container, be heated to 80 ℃, add cadmium acetate, ammonium acetate, ammoniacal liquor, deposit thickness is about 100nm.
The light-absorption layer preparation: nearly vacuum sublimation legal system is equipped with the CdTe film, and underlayer temperature is 500 ℃, and argon gas or argon oxygen gas mixture are as carrier gas, and reaction pressure 1kPa, evaporation source are CdTe, and deposit thickness is about 7 μ m.
Barrier layer preparation: adopt sputtering method to prepare the ZnTe/ZnTe:Cu composite bed, above-mentioned underlayer temperature is 300 ℃, reaction pressure is 0.1Pa, power is 100W, argon gas or argon oxygen gas mixture are as carrier gas, gas flow 5sccm, target are ZnTe target and ZnTe:Cu, and deposit thickness is respectively 20nm and 70nm.
The back-contact electrode preparation: pour Kynoar (PVDF) solvent into container, adopt magnetic agitation, be heated to 80 ℃, adding 1-Methyl-2-Pyrrolidone (NMP) solvent is adhesive, the about 20g/L of concentration.Mix through stirring fully.The Cu powder that mixes 6%wt fully stirs.The siccative average mark adds Graphene four times, and each 28-32 minute at interval, fully stir, obtain thick Graphene slurry.After graphite slurry fully stirred, battery front side is pasted blue film protection, immerse graphite slurry, lift, take off and be placed on 150 ° of c oven for drying, peel off positive blue film, finish battery unit structure with 2mm/s speed.Transformation efficiency is shown in Fig. 5 (c), and all the other are with embodiment 1.
Claims (9)
1. the back-contact electrode in the CdTe film solar battery structure comprises transparent conducting glass layer, Window layer, light-absorption layer, barrier layer successively, it is characterized in that preparing the graphene film layer as back-contact electrode at the back side, barrier layer.
2. by the described back-contact electrode of claim 1, the thickness that it is characterized in that described graphene layer is 0.1 μ m-1mm.
3. by the described back-contact electrode of claim 1, it is characterized in that:
1. conductive glass layer
Electro-conductive glass is a tin-doped indium oxide, Al-Doped ZnO or fluorine doped tin oxide glass, the thickness 1mm～3mm of glass substrate, above the thickness of conductive layer be 300nm～3 μ m;
2. Window layer
Window layer is a cadmium sulfide, and thickness is 20nm～300 μ m;
3. light-absorption layer
Light-absorption layer is a cadmium telluride, and thickness is at 600nm～10 μ m;
4. barrier layer
The barrier layer is a zinc telluridse/mix copper zinc telluridse composite bed, and its thickness is between 5nm～500nm; Or being tellurium mercury/mix copper tellurium mercury composite bed, thickness is 5nm～500nm.
4. the method for preparing back-contact electrode as claimed in claim 1 or 2, comprise the preparation on conductive glass layer, Window layer, light-absorption layer, barrier layer successively, it is characterized in that adding adhesive and prepare the Graphene slurry in Graphene, be prepared into graphene layer by the Graphene slurry then, concrete steps are:
A) adopting Kynoar is solute, and 1-Methyl-2-Pyrrolidone is a solvent, presses 0.01g/ml to 1g/ml proportional arrangement adhesive;
B) mixed liquor of the adhesive that step a) is disposed fully mixes through stirring;
C) Graphene is inserted b) in the adhesive of preparation the addition of Graphene be 0.01g/ml to 100g/ml, through fully stirring, obtain thick Graphene slurry;
D) the Graphene slurry that step c) is made prepares the graphene film layer by printing, spin coating or method of pulling up at the back side on CdTe battery barrier layer, as battery contact back electrode.
5. by the described preparation method of claim 4, when it is characterized in that having resistive formation between the transparent conducting glass of the CdTe battery for preparing and the Window layer, then in the Graphene slurry, add 1-40wt%Cu or HgTe:Cu, and fully stir.
6. by the described preparation method of claim 4, when it is characterized in that the steps d spin coating battery is placed on the spin coater, vacuum suction is fixed, and after the Graphene slurry is fully stirred, is poured on cell backside and adopts two step spin coatings, dries after the spin coating.
7. by the described preparation method of claim 4; it is characterized in that the described czochralski method of steps d is that the Graphene slurry that will prepare pastes the protection of blue film with battery front side after fully stirring; immerse in the Graphene slurry, lift, peel off positive blue film after taking off oven dry with 2mm/s speed.
8. by claim 6 or 7 described preparation methods, it is characterized in that bake out temperature is 150 ℃.
9. by the described preparation method of claim 1, when it is characterized in that the barrier layer does not exist, then graphene film directly prepares at the light-absorption layer back side, as back-contact electrode.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2009085224A2 (en) * | 2007-12-20 | 2009-07-09 | Cima Nanotech Israel Ltd. | Photovoltaic device having transparent electrode formed with nanoparticles |
| US20090235986A1 (en) * | 2008-03-18 | 2009-09-24 | Solexant Corp | Back contact for thin film solar cells |
-
2010
- 2010-11-11 CN CN201010541026.9A patent/CN102074590B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2009085224A2 (en) * | 2007-12-20 | 2009-07-09 | Cima Nanotech Israel Ltd. | Photovoltaic device having transparent electrode formed with nanoparticles |
| US20090235986A1 (en) * | 2008-03-18 | 2009-09-24 | Solexant Corp | Back contact for thin film solar cells |
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