CN102544189A - Thin film solar cell and manufacturing method thereof - Google Patents
Thin film solar cell and manufacturing method thereof Download PDFInfo
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- CN102544189A CN102544189A CN2010105902028A CN201010590202A CN102544189A CN 102544189 A CN102544189 A CN 102544189A CN 2010105902028 A CN2010105902028 A CN 2010105902028A CN 201010590202 A CN201010590202 A CN 201010590202A CN 102544189 A CN102544189 A CN 102544189A
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Abstract
A manufacturing method of a thin film solar cell comprises the steps of preparing a substrate firstly, then forming a thin film cell layer on the substrate, subsequently, preparing a graphene transition layer on the thin film cell layer, and finally, forming a back metal electrode on the transition layer. The invention also provides a thin film solar cell. According to the cell manufactured with the method disclosed by the invention and the thin film solar cell disclosed by the invention, a good ohmic contact is formed between the thin film cell layer and the back metal electrode.
Description
[technical field]
The present invention relates to solar battery technology, relate in particular to a kind of thin film solar cell and preparation method thereof.
[background technology]
Cadmium telluride (CdTe) is the II-VI group iii v compound semiconductor material; Its electron affinity is 4.28eV; Work function is generally more than 5.5eV; And usually as the work function of metals such as the Au of back electrode, Ag, Cu, Al, Ni, Mo generally all less than 5eV, the work function of cadmium telluride is higher than conventional back electrode material.According to Semiconductive Theory, make semi-conducting material and metal have good Ohmic contact, the work function of metal must be greater than the work function of semi-conducting material.As the II-VI compounds of group, cadmium telluride has the self compensation effect, makes to be difficult to through the existing conventional technology it carried out heavy doping.
Above-mentioned situation causes that the ohmic contact characteristic between the Cadimium telluride thin film and metal back electrode becomes one of difficult point in the cadmium telluride battery production process in the cadmium telluride battery.
For reducing contact berrier and the improvement ohmic contact characteristic between the two between Cadimium telluride thin film and the metal back electrode, the existing common way of industry is between Cadimium telluride thin film and metal back electrode, to add transition zone.Buffer layer material there is following requirement: 1) as the material of transition zone; Its top of valence band position will be lower than the top of valence band of cadmium telluride or be in same position basically with the top of valence band of cadmium telluride, thereby avoids interface zone the valence band spike that the hole transports to back electrode to occur hindering; 2) material of this transition zone can be realized heavy doping.Satisfy the material that above-mentioned requirements can be used as transition zone zinc telluridse (ZnTe) arranged, mix copper zinc telluridse (ZnTe:Cu), tellurium mercury (HgTe), molybdenum nitrogen alloy (Mo:N) etc.
P.W.Meyers at first uses heavily doped P-ZnTe as the transition zone between cadmium-telluride layer and metal electrode.But as the II-VI compounds of group, cadmium telluride has the self compensation effect, and it is bigger that it is carried out the heavy doping technology difficulty.
After this, also there are some researchers to use diverse ways, the preparation of polycrystalline ZnTe film studied like evaporation, sputtering method, electrochemical deposition method etc.People such as R.G.Born have studied the ZnTe film of sputtering method preparation, have realized mixing with Cu and N, make it to become P type semiconductor.Human sputtering methods such as T.A.Gerssert have prepared the ZnTe film of mixing Cu, have studied the relation of conductivity and underlayer temperature, and when finding that underlayer temperature is higher than 260 ℃ of left and right sides, conductivity reduces significantly.
But the phenomenon that distributes again can appear spreading in the copper in the above-mentioned transition zone that is doped with copper under electric field action, thereby can cause battery performance to descend.High-octane ion bombardment meeting produces more electroactive defective in the sputtering method in addition, can reduce battery efficiency.
[summary of the invention]
In view of this, the present invention provides a kind of thin film solar cell and preparation method thereof, to address the above problem.
Thin film solar cell preparation method of the present invention comprises the preparation substrate, on said substrate, forms the hull cell layer, and preparation Graphene transition zone forms back of the body metal electrode on said Graphene transition zone on said hull cell layer.
Thin film solar cell preparation method of the present invention; Preferably; Said hull cell layer is the Cadimium telluride thin film layer; Range upon range of cadmium sulfide and Cadimium telluride thin film layer, or range upon range of high resistant intrinsic layer, cadmium sulfide and Cadimium telluride thin film layer, wherein said back of the body metal electrode is formed on the said Cadimium telluride thin film layer.
Thin film solar cell preparation method of the present invention preferably, prepares said Graphene transition zone and further comprises through the preparation Graphene, through the high temperature transfer method prepared graphene is transferred to said hull cell layer formation Graphene transition zone.
Thin film solar cell preparation method of the present invention preferably, prepares Graphene through chemical vapour deposition technique, oxidation attenuate graphite flake method, tear tape method, silicon carbide epitaxy, metal surface growth method.
Thin film solar cell preparation method of the present invention, preferably, said Graphene transition zone can be single-layer graphene or multi-layer graphene.
Thin film solar cell preparation method of the present invention, preferably, the material of said back of the body metal electrode is any one the perhaps any multiple formed alloy material among Au, Ag, Al, Ni, the Mo.
Thin film solar cell preparation method of the present invention, preferably, said substrate is a conductive film glass.
The present invention also provides a kind of thin film solar cell, comprise substrate, successively be formed on the substrate the hull cell layer and the back of the body metal electrode, be the Graphene transition zone between said hull cell layer and the said back of the body metal electrode.
Said thin film solar cell, preferably, said Graphene transition zone is single-layer graphene or multi-layer graphene.
Said thin film solar cell; Preferably; Said hull cell layer is Cadimium telluride thin film layer, range upon range of cadmium sulfide and Cadimium telluride thin film layer or range upon range of high resistant intrinsic layer, cadmium sulfide and Cadimium telluride thin film layer, and wherein said back of the body metal electrode is formed on the said Cadimium telluride thin film layer.
Said thin film solar cell, preferably, the material of said back of the body metal electrode is any one the perhaps any multiple formed alloy material among Au, Ag, Al, Ni, the Mo.
Said thin film solar cell, preferably, said substrate is a conductive film glass.
Have the Graphene transition zone through method prepared film solar cell of the present invention, thereby increased the ohmic contact characteristic of prepared cell, Graphene transition zone manufacture craft is simple and reliable in addition.Equally, thin film solar cell of the present invention is because the Graphene transition zone, thereby good Ohmic contact characteristic between hull cell layer and the back of the body metal electrode is provided.
[description of drawings]
Fig. 1 is of the present invention with the structural representation of Graphene as the cadmium telluride battery of transition zone
[embodiment]
Need to prove; The following execution mode of the present invention is with thin film solar cell; Especially manufacturing and the structure with the Cadimium telluride thin film battery is the explanation that example is carried out, but the present invention is not limited to this at this point, and the present invention also can be applicable in other battery manufacturing or the structure.
At first, clean transparent conductive film (TCO) glass to remove its lip-deep spot, for example oil stain and dust particle etc.In this execution mode, the thickness of this conductive film glass can arrive 4mm for 1mm; Conductive film glass can adopt mix in arsenic indium oxide (ITO), Al-Doped ZnO (ZnO:Al), the fluorine doped tin oxide (SnO2:F) any one or be their compound.
Then, deposition high resistant intrinsic layer (HRT) layer; Specifically can be, through methods such as magnetron sputtering, heat deposition, deposition 200nm left and right thickness by zinc oxide (ZnO), titanium dioxide arsenic (SnO
2) or silicon dioxide (SiO
2) wait formed native oxide layer.In the present embodiment, methods such as magnetron sputtering and heat deposition are this area routine techniques, do not do at this and give unnecessary details.
Subsequently, on the high resistant intrinsic layer, deposit long-pending Cadmium arsenide (CdS) Window layer through methods such as near space distillation (CSS), magnetron sputtering, heat deposition; According to present embodiment, the thickness of this Window layer is about 100nm.
Afterwards, prepare the Cadimium telluride thin film battery layers through gas phase transmission deposition (VTD), near space distillation or electrochemical deposition membrane deposition methods such as (ECD).According to the embodiment of the present invention, the thickness of this hull cell layer can be made for 2～4 μ m.
After this Cadimium telluride thin film battery layers preparation, contain dichloride cadmium (CdCl
2) heat treatment under the atmosphere.For instance, let the Cadimium telluride thin film battery layers that has prepared contain dichloride cadmium (CdCl
2) the chlorine atmosphere under keep about 30 minutes of temperature about 400 ℃, carry out annealing in process with this.
After heat treatment, the Cadimium telluride thin film battery layers that has prepared is carried out chemical corrosion, so that be rich in tellurium on the surface of Cadimium telluride thin film battery layers.Chemical corrosion solution can be phosphoric acid nitric acid mixed liquor, acetate nitric acid mixed liquor etc.
Through after the chemical corrosion, at Cadimium telluride thin film battery layers surface preparation Graphene transition zone.For the preparation of Graphene transition zone, can carry out as follows: prepare Graphene through the chemical vapor deposition (CVD) method; With the high temperature transfer method prepared graphene is transferred to Cadimium telluride thin film battery layers surface again and form graphene layer.Graphene layer can be a duplicature, can be monofilm also, and this depends on actual needs; Generally speaking the thickness of graphene layer is to be no more than 50 layers for good.Alternatively, Graphene also can adopt modes such as oxidation attenuate graphite flake, tear tape method, silicon carbide epitaxy, metal surface growth method to process.
After the graphene layer preparation finishes, on the graphene layer that has prepared, form back of the body metal electrode through methods such as magnetically controlled sputter method, heat deposition, electron beam depositions; Wherein, generally select for use Au, Ag, Al, Ni, Mo any or arbitrarily multiple formed alloy process the back electrode metal level.
Through said method, prepared graphene layer at back of the body metal electrode and Cadimium telluride thin film battery layers.Based on the following characteristic of Graphene, form good Ohmic contact between back of the body metal electrode and the Cadimium telluride thin film battery layers, and then improved the diode effect of battery, significantly reduce series resistance, improve the conversion efficiency of CdTe battery.The characteristic of said Graphene comprises:
1. graphene-structured is highly stable.In the Graphene, the connection between each carbon atom is very pliable and tough, and when applying external mechanical force, the carbon atom face adapts to external force with regard to flexural deformation thereby carbon atom needn't be arranged again, therefore can keep its original structure, that is Stability Analysis of Structures.
2. the interference that receives of the electronics in the Graphene is little.In the graphene-structured, when electronics moves in track, can or not introduce foreign atom scattering takes place because of lattice defect; Because active force is strong between its atom, make under the normal temperature, even it is carbon atom telescopes on every side, also very little to the interference that the electronics in the Graphene receives.
3. electronic movement velocity is high in the Graphene, can reach 1/300 of the light velocity.
4. Graphene has very high intensity, and the maximum pressure that can bear on every 100nm distance has reached about 2.9 μ N.
5. Graphene is not having under the spin(-)orbit coupling, is no energy gap owing to receive the symmetric protection of sixfold, electron spectrum.When considering the spin(-)orbit coupling, its energy gap will be opened, but big I is ignored the energy gap 0.000001eV that the spin(-)orbit coupling is induced in the grapheme material.Be easier to change the conduction type of Graphene through doping.
Fig. 1 is of the present invention with the structural representation of Graphene as the cadmium telluride battery of transition zone.Need to prove that this figure is the relativeness in order to illustrate between each layer only, the length or the thickness that do not limit each layer shown in figure at this point.
Like diagram, said cadmium telluride battery comprises substrate 10, high resistant intrinsic layer 12, Cadmium arsenide's layer 14, Cadimium telluride thin film battery layers 16, transition zone 18, and back electrode metal level 20.
In this example, substrate 10 is a conductive film glass, and its thickness for example arrives 4mm for 1mm.Particularly, conductive film glass can adopt mix in arsenic indium oxide, Al-Doped ZnO, the fluorine doped tin oxide any one or be their compound.The high resistant intrinsic layer 12 that is prepared on the substrate 10 can be to be deposited on the substrate 10 through methods such as magnetron sputtering, heat deposition, and thickness can as an example, can form high resistant intrinsic layer 12 by zinc oxide, titanium dioxide arsenic or silicon dioxide for about 200nm.The Cadmium arsenide's layer 14 that is deposited on the high resistant intrinsic layer 12 can pass through method preparations such as near space distillation, magnetron sputtering, heat deposition, and its thickness can for example be 100nm.Simultaneously, the Cadimium telluride thin film battery layers 16 that is deposited on Cadmium arsenide's layer 14 can prepare through membrane deposition methods such as gas phase transmission deposition, near space distillation or electrochemical depositions, and its thickness is preferably 2～4 μ m.The Cadimium telluride thin film battery layers can be passed through chemical corrosion so that be rich in tellurium on its surface for 16 layers.Transition zone 18 is formed by graphene layer, and its formation at first prepares Graphene through chemical gaseous phase depositing process; Thereby the surface of with the high temperature transfer method prepared graphene being transferred to Cadimium telluride thin film battery layers 16 again forms Graphene transition zone 18.On transition zone 18, be provided with through methods such as magnetically controlled sputter method, heat deposition, electron beam depositions and on the graphene layer that has prepared, form back of the body metal electrode 20.The material of back electrode metal level is generally selected Au, Ag, Al, Ni, Mo and alloy thereof for use.
As CdTe battery back electrode transition layer, can effectively improve CdTe layer and the ohmic contact characteristic of carrying on the back metal electrode by Graphene, improve the collection characteristic of electric current, thereby reach the purpose that improves battery conversion efficiency.Simultaneously, utilize Graphene, can also improve CdTe battery and the mechanical property of carrying on the back metal electrode as CdTe battery back of the body contact transition zone.
Compare with the structure of the cadmium telluride battery described in Fig. 1, in other embodiment of the present invention, the cadmium telluride battery can not comprise high resistant intrinsic layer 12 and/or Cadmium arsenide's layer 14.
At last, should be noted that above embodiment is only in order to technical scheme of the present invention to be described but not limit it.Although the present invention has been carried out detailed explanation with reference to above-mentioned embodiment; Those of ordinary skill in the art is to be understood that; Still can specific embodiments of the invention make amendment or the part technical characterictic is equal to replacement; And under the spirit that does not break away from technical scheme of the present invention, it all should be encompassed in the middle of the technical scheme scope that the present invention asks for protection.
Claims (12)
1. a thin film solar cell preparation method is characterized in that, said method comprises: the preparation substrate, on said substrate, form the hull cell layer, and preparation Graphene transition zone forms back of the body metal electrode on said Graphene transition zone on said hull cell layer.
2. thin film solar cell preparation method according to claim 1; It is characterized in that; Said hull cell layer is the Cadimium telluride thin film layer; Range upon range of cadmium sulfide and Cadimium telluride thin film layer, or range upon range of high resistant intrinsic layer, cadmium sulfide and Cadimium telluride thin film layer, wherein said back of the body metal electrode is formed on the said Cadimium telluride thin film layer.
3. according to right 1 or 2 described thin film solar cell preparation methods; It is characterized in that; Prepare said Graphene transition zone and further comprise the preparation Graphene, and prepared graphene is transferred to formation Graphene transition zone on the said hull cell layer through the high temperature transfer method.
4. according to right 3 described thin film solar cell preparation methods, it is characterized in that, prepare Graphene through chemical vapour deposition technique, oxidation attenuate graphite flake method, tear tape method, silicon carbide epitaxy, metal surface growth method.
5. according to right 1 or 2 described thin film solar cell preparation methods, it is characterized in that said Graphene transition zone is single-layer graphene or multi-layer graphene.
6. thin film solar cell preparation method according to claim 1 and 2 is characterized in that, the material of said back of the body metal electrode is any one or any multiple formed alloy among Au, Ag, Al, Ni, the Mo.
7. according to the said thin film solar cell preparation method of claim 1, it is characterized in that said substrate is a conductive film glass.
8. thin film solar cell that thin film solar cell preparation method according to claim 1 processes; Comprise substrate, successively be formed on the substrate the hull cell layer and the back of the body metal electrode; It is characterized in that, be the Graphene transition zone between said hull cell layer and the said back of the body metal electrode.
9. thin film solar cell according to claim 8 is characterized in that, said Graphene transition zone is single-layer graphene or multi-layer graphene.
10. according to Claim 8 or 9 described thin film solar cells; It is characterized in that; Said hull cell layer is Cadimium telluride thin film layer, range upon range of cadmium sulfide and Cadimium telluride thin film layer or range upon range of high resistant intrinsic layer, cadmium sulfide and Cadimium telluride thin film layer, and wherein said back of the body metal electrode is formed on the said Cadimium telluride thin film layer.
11. according to Claim 8 or 9 described thin film solar cells, it is characterized in that the material of said back of the body metal electrode is any one or the multiple formed alloy arbitrarily among Au, Ag, Al, Ni, the Mo.
12. according to Claim 8 or 9 described thin film solar cells, it is characterized in that said substrate is a conductive film glass.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103227241A (en) * | 2013-04-10 | 2013-07-31 | 苏州阿特斯阳光电力科技有限公司 | Preparation method of double-faced crystalline silicon solar cell |
| CN104124290A (en) * | 2014-07-24 | 2014-10-29 | 四川大学 | Cadmium telluride solar cell with Te-Ti-Cu pre-set layer |
| CN104241439A (en) * | 2013-06-09 | 2014-12-24 | 北京恒基伟业投资发展有限公司 | Method for preparing cadmium telluride thin-film solar cell |
| CN105355674A (en) * | 2015-07-20 | 2016-02-24 | 四川大学 | Flexible cadmium telluride solar cell with graphene insertion layer |
| CN106952864A (en) * | 2016-01-06 | 2017-07-14 | 中芯国际集成电路制造(上海)有限公司 | Interconnection structure and forming method thereof, integrated circuit |
| WO2018119682A1 (en) * | 2016-12-27 | 2018-07-05 | China Triumph International Engineering Co., Ltd. | Method for producing a cdte thin-film solar cell |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101299443A (en) * | 2008-06-17 | 2008-11-05 | 四川大学 | Flexible cadmium telluride thin-film solar cell structure |
| CN101609860A (en) * | 2009-07-16 | 2009-12-23 | 上海联孚新能源科技有限公司 | CdTe thin-film solar cells preparation method |
-
2010
- 2010-12-14 CN CN2010105902028A patent/CN102544189A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101299443A (en) * | 2008-06-17 | 2008-11-05 | 四川大学 | Flexible cadmium telluride thin-film solar cell structure |
| CN101609860A (en) * | 2009-07-16 | 2009-12-23 | 上海联孚新能源科技有限公司 | CdTe thin-film solar cells preparation method |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103227241A (en) * | 2013-04-10 | 2013-07-31 | 苏州阿特斯阳光电力科技有限公司 | Preparation method of double-faced crystalline silicon solar cell |
| CN104241439A (en) * | 2013-06-09 | 2014-12-24 | 北京恒基伟业投资发展有限公司 | Method for preparing cadmium telluride thin-film solar cell |
| CN104124290A (en) * | 2014-07-24 | 2014-10-29 | 四川大学 | Cadmium telluride solar cell with Te-Ti-Cu pre-set layer |
| CN104124290B (en) * | 2014-07-24 | 2017-01-11 | 四川大学 | Cadmium telluride solar cell with Te-Ti-Cu pre-set layer |
| CN105355674A (en) * | 2015-07-20 | 2016-02-24 | 四川大学 | Flexible cadmium telluride solar cell with graphene insertion layer |
| CN106952864A (en) * | 2016-01-06 | 2017-07-14 | 中芯国际集成电路制造(上海)有限公司 | Interconnection structure and forming method thereof, integrated circuit |
| WO2018119682A1 (en) * | 2016-12-27 | 2018-07-05 | China Triumph International Engineering Co., Ltd. | Method for producing a cdte thin-film solar cell |
| CN108513683A (en) * | 2016-12-27 | 2018-09-07 | 中国建材国际工程集团有限公司 | Method for producing CdTe thin film solar cell |
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Application publication date: 20120704 |