CN103426974A - Substrate with p-type amorphous silicon and transparent conductive oxide film and preparation method - Google Patents
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- CN103426974A CN103426974A CN2012101578537A CN201210157853A CN103426974A CN 103426974 A CN103426974 A CN 103426974A CN 2012101578537 A CN2012101578537 A CN 2012101578537A CN 201210157853 A CN201210157853 A CN 201210157853A CN 103426974 A CN103426974 A CN 103426974A
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Abstract
The invention provides a substrate with p-type amorphous silicon and a transparent conductive oxide film and a preparation method. The method includes the steps that a substrate with the transparent conductive oxide film is prepared; textures are formed on the surface of the substrate with the transparent conductive oxide film to obtain a substrate with a texture surface structure and the transparent conductive oxide film; a physical vapor deposition (PVD) method is used for forming an amorphous silicon p-type layer on the substrate with the texture surface structure and the transparent conductive oxide film, and the substrate with the p-type amorphous silicon and the transparent conductive oxide film is obtained. The PVD is used for forming the amorphous silicon p-type layer, so that reprocessing needed for oxidizing the substrate with the transparent conductive oxide film is avoided, follow-up application is simple and convenient, and cost is reduced observably.
Description
Technical field
The invention relates to a kind of process that is applied to solar cell, espespecially a kind of method and preparation method who prepares the substrate with p-type uncrystalline silicon and transparent conductive oxide film.
Background technology
General glass dealer can be at tin oxide (Fluorine doped Tin Oxide, FTO, the SnO that mixes fluorine that first plate on glass
2: F) film, sell again the amorphous silicon thin-film solar cell dealer, Fig. 4 a and Fig. 4 b are depicted as the main flow of a kind of amorphous silicon thin-film solar cell of prior art and make flow process, the dotted line circle means the technique of glass dealer end, by the first complete glass substrate 50 of glass dealer, deposit again FTO film 60 on glass substrate 50, then by the glass substrate 50(of this deposition FTO film 60 hereinafter referred to as FTO glass) sell the solar cell dealer, the solar cell dealer is after buying FTO glass, first cleaned (wet cleaning) operation, and then with plasma formula chemical vapour deposition (CVD) (plasma enhanced chemical vapor deposition, PECVD) board is by uncrystalline silicon p-type layer 70 (p-type layer), uncrystalline silicon intrinsic layer 80 (i-type layer) and uncrystalline silicon N-shaped layer (n-type layer) sequentially are deposited on and clean FTO glass substrate later, and continue and plate contact layer and electrode layer dorsad, to complete the making of amorphous silicon thin-film solar cell.The shortcoming of this technique is that the manufacturing cost of FTO film is too high, glass substrate 50 prices that make to have FTO film 60 are high, account for 30 percent of total manufacturing cost, and the existing patent of this technique monopolizes problem, be unable to cope with the solar cell market that price competition is growing more intense.
Therefore, for reducing costs, refer to shown in Fig. 5 a Fig. 5 b, the segment glass dealer adopts another manufacture method, attempt makes other material replace FTO to reduce production costs, the dotted line circle means the technique of glass dealer end, it is to utilize PECVD or physical vapour deposition (PVD) (physical vapor deposition, PVD) deposit transparent conductive oxide (Transparent Conductive Oxide voluntarily, TCO) film, aluminum zinc oxide (Aluminum doped zinc oxide, AZO, ZnO:Al for example
2O
3) film 100, to replace FTO film 60, and then reduce the cost of glass substrate 90.Yet, FTO film 60 can be convenient to subsequent thin film formation by self-forming texture (texture) surface texture after being deposited on glass substrate 50, but while using AZO film 100 to replace FTO film 60, after the glass dealer need to deposit AZO film 100 on glass substrate 90, then could obtain the grain surface structure similar to FTO through a wet etching etching technique.Concrete, after 90s by the complete glass substrate of glass dealer, first deposit AZO film 100 on glass substrate 90, then with approximately 0.5% salt acid dip (wet dipping) of concentration, in order to form the grain surface structure on AZO film 100, then sell the solar cell dealer by this impregnated AZO glass, the solar energy dealer is after complete this AZO glass, equally first cleaned (wet cleaning) operation, the follow-up making that completes again amorphous silicon thin-film solar cell with identical making flow process, , with plasma formula chemical vapour deposition (CVD) (plasma enhanced chemical vapor deposition, PECVD) board deposited amorphous matter silicon p-type layer (p-type layer) 110 sequentially, the follow-up making flow processs such as uncrystalline silicon intrinsic layer (i-type layer) 120 and uncrystalline silicon N-shaped layer (n-type layer).Yet, the shortcoming of this operation is that AZO film 100 is after the pickling dipping, easy adsorb oxygen and aqueous vapor, and there will be the problem of storing for a long time and causing resistance to increase, and then affect conductivity and stability, have serious impact for the solar energy conversion efficiency, so just can make glass substrate 90 damage rates with AZO film 100 improve, the cost of glass dealer end is increased.
Summary of the invention
Because in prior art, previously prepared FTO glass high cost, and AZO glass needs extra routine processes in follow-up use, and stored and have for a long time the problem that resistance increases, AZO glass substrate damage rate is improved, and then cost is increased.In addition; in prior art; mainly to utilize PECVD that uncrystalline silicon p-type layer is deposited on this substrate with transparent conductive oxide film with grain surface structure; because of this uncrystalline silicon p-type layer better compared to the character of the formed uncrystalline silicon p-type of PVD layer; yet the instrument cost of PVD is far below the instrument of PECVD; if the glass dealer in order to protect AZO film in the glass substrate with AZO film to avoid adsorb oxygen and aqueous vapor wish use PECVD first to form uncrystalline silicon p-type layer on this AZO film the time, to cost, be also a kind of burden.Therefore, the invention provides a kind of method for preparing the substrate with p-type uncrystalline silicon and transparent conductive oxide film, and a kind of substrate (hereinafter referred to as the p-Si/TCO substrate) with p-type amorphous silicon thin-film and transparent conductive oxide film obtained by this method is provided, it has the effect significantly reduced costs.
The method that has the substrate of p-type uncrystalline silicon and transparent conductive oxide film according to preparation of the present invention comprises the following steps:
Complete one has the substrate (hereinafter referred to as the TCO substrate) of transparent conductive oxide film;
Surface in this TCO substrate forms texture, obtains a TCO substrate with grain surface structure; And
Use sputtering method to form a uncrystalline silicon p-type layer on this has the TCO substrate of grain surface structure, obtain a substrate (p-Si/TCO substrate) with p-type amorphous silicon thin-film and transparent conductive oxide film;
The polysilicon target that the target wherein used in sputtering method is doped with boron.
Preferably, wherein the step of complete this TCO substrate more comprises a first complete base material; Deposition one transparent conductive oxide film on this base material.
According to the present invention, base material of the present invention includes, but are not limited to: glass baseplate, stainless steel substrate, plastic rubber substrate or ceramic base material etc.
Preferably, wherein in the surface of this TCO substrate, form texture, obtain a TCO substrate with grain surface structure, it is to use an acid solution to flood this TCO substrate.
Preferably, at this, have on the TCO substrate of grain surface structure and use physical vaporous deposition to form a uncrystalline silicon p-type layer, obtain a p-Si/TCO substrate.
Preferably, wherein transparent conductive oxide film is the aluminum zinc oxide film.
Preferably, wherein this physical vaporous deposition is sputtering method.
Another object of the present invention is that a kind of substrate (p-Si/TCO substrate) with p-type amorphous silicon thin-film and transparent conductive oxide film is being provided, its structure at least includes a substrate, a transparent conductive oxide film and a p-type amorphous silicon thin-film, and this p-Si/TCO substrate is to be made by above-mentioned manufacture method.
According to the present invention, base material of the present invention includes, but are not limited to: glass baseplate, stainless steel substrate, plastic rubber substrate or ceramic base material etc.
Preferably, wherein base material is glass baseplate.
Preferably, wherein transparent conductive oxide film is the aluminum zinc oxide film.
Preferably, wherein transparent conductive oxide film has the grain surface structure.
The invention has the advantages that, flood this TCO substrate in using an acid solution, obtain one there is the TCO substrate of grain surface structure after, continue and utilize PVD that uncrystalline silicon p-type layer is deposited on this TCO substrate with grain surface structure, this uncrystalline silicon p-type layer is used as to a secluding film, using isolated this TCO film contacts with atmosphere, thereby prevent the problem that resistance increases, especially when this TCO film is the AZO film, so not only solve the AZO film because storing the problem that causes resistance to increase and then damage rate is improved for a long time, more used the PVD instrument replacement PECVD instrument that price is lower similar to the uncrystalline silicon p-type layer character of using PECVD to manufacture to form uncrystalline silicon p-type layer and to manufacture its property system of uncrystalline silicon p-type layer, the cost that can also reduce by more than 50 than the glass substrate of FTO film in prior art.In addition, the glass dealer is in using p-Si/TCO base plate preparation method of the present invention, form in advance uncrystalline silicon p-type layer, just can reduce job step of solar cell dealer, only need after cleaning this p-Si/TCO substrate, utilize the PECVD board to carry out the hydrogen plasma cleaning to p-type noncrystalline silicon layer surface, therefore the quite economic benefit.
The accompanying drawing explanation
Fig. 1 a is technological process of the present invention.
Fig. 1 b is technological process of the present invention.
The contrast figure of power-voltage and current that Fig. 2 is the solar cell prepared of the present invention-voltage.
The contrast figure of power-voltage and current that Fig. 3 is the solar cell prepared of prior art-voltage.
The technological process of the glass substrate of the uncrystalline silicon FTO film that Fig. 4 a is one of prior art.
The technological process of the glass substrate of the uncrystalline silicon FTO film that Fig. 4 b is one of prior art.
The technological process of the glass substrate of the uncrystalline silicon AZO film that Fig. 5 a is one of prior art.
The technological process of the glass substrate of the uncrystalline silicon FTO film that Fig. 5 b is one of prior art.
Drawing reference numeral:
10 base material 20 transparent conductive oxide films
30 uncrystalline silicon p-type layer 40 uncrystalline silicon intrinsic layer
50 glass substrate 60FTO films
70 uncrystalline silicon p-type layer 80 uncrystalline silicon intrinsic layer
90 glass substrate 100AZO films
110 uncrystalline silicon p-type layer 120 uncrystalline silicon intrinsic layer
Embodiment
Preparation of the present invention has the method for the substrate of p-type uncrystalline silicon and transparent conductive oxide film, and it comprises the following steps:
A complete base material;
On this base material, deposition one transparent conductive oxide film, use a complete TCO substrate;
Use an acid solution to flood this TCO substrate, obtain a TCO substrate with grain surface structure;
Have on the TCO substrate of grain surface structure and form a uncrystalline silicon p-type layer (p-type layer) at this, obtain a p-Si/TCO substrate;
The present invention will be by following embodiment as further illustrating, and these embodiment do not limit the content that disclose front of the present invention.
Embodiment
Embodiment 1: refer to shown in Fig. 1 a Fig. 1 b, the preparation of a preferred embodiment of the present invention has the method for the substrate of p-type uncrystalline silicon and transparent conductive oxide film, comprises the following steps:
A complete base material 10, this base material 10 is glass baseplate;
Using a weight proportion of composing is ZnO:Al
2O
3The AZO target of=98:2 deposits the transparent conductive oxide film 20 that a thickness is 1 micron (μ m) on this base material 10, and this transparent conductive oxide film 20 is the AZO film, obtains an AZO substrate; Use one 0.5% hydrogen chloride solution to flood this AZO substrate, obtain an AZO substrate with grain surface structure;
At the temperature of using sputtering method and being 350 ° of C in a substrate temperature, have on the AZO substrate of grain surface structure and form a uncrystalline silicon p-type layer 30(p-type layer at this), obtain a p-Si/TCO substrate, the target wherein used in sputter procedure is the polysilicon target doped with boron.
This p-Si/TCO substrate was placed in atmospheric environment after seven days, this p-Si/TCO substrate is cleaned;
Re-use PECVD this p-Si/TCO substrate is carried out to the hydrogen plasma cleaning, and sequentially form uncrystalline silicon intrinsic layer 40 and uncrystalline silicon N-shaped layer on this uncrystalline silicon p-type layer 30, technological temperature is about 200 ° of C.
Embodiment 2: the present invention compared with the prior art
Use the photoelectric characteristic of this uncrystalline silicon p-type layer of the substrate with transparent conductive oxide film of the prepared uncrystalline silicon of the method for the substrate with transparent conductive oxide film for preparing uncrystalline silicon of the present invention, with the comparison of the photoelectric characteristic of this uncrystalline silicon p-type layer of the substrate with transparent conductive oxide film of the prepared uncrystalline silicon of prior art, as shown in table 1.Wherein use the method for prior art to use PECVD, and adopt the silane (H of diluted in hydrogen
2+ SiH
4) and doping borine (B
2H
6) gas is with the uncrystalline silicon p-type layer in the substrate with transparent conductive oxide film of preparing uncrystalline silicon.
Table 1: the photoelectric characteristic of the uncrystalline silicon p-type layer of the substrate with transparent conductive oxide film of the uncrystalline silicon of the present invention and prior art
S/cm: every centimeter of Siemens
EV: electronvolt
When the thickness of uncrystalline silicon p-type layer is all 70A, can learn that the photoelectric characteristics such as its dark conductance, photoconduction and energy gap are comparable to this uncrystalline silicon p-type layer of the substrate with transparent conductive oxide film of the prepared uncrystalline silicon of prior art by this uncrystalline silicon p-type layer of the substrate with transparent conductive oxide film of the prepared uncrystalline silicon of the present invention.Wherein measure dark conductance and photoconduction use electric property measurement system.
Embodiment 3: the comparison of the solar cell that uses the present invention and prior art to prepare
3.1 use p-Si/TCO base plate preparation method of the present invention to prepare solar cell of the present invention
Method of the present invention can be applicable to the making of amorphous silicon thin-film solar cell, and the step of a preferred embodiment comprises:
As the preparation method of embodiment mono-obtains a p-Si/TCO substrate;
This p-Si/TCO substrate was placed in atmospheric environment after seven days, this p-Si/TCO substrate is cleaned;
Again the p-Si/TCO substrate is placed in to the PECVD board and carries out the hydrogen plasma cleaning, and sequentially form uncrystalline silicon intrinsic layer on this uncrystalline silicon p-type layer, and doping phosphine (PH
3) gas, forming a uncrystalline silicon N-shaped layer in this uncrystalline silicon intrinsic layer, technological temperature is about 200 ° of C;
Using a weight proportion of composing is ZnO:Al
2O
3The AZO target of=98:2 deposits the AZO film that a thickness is 1800A on uncrystalline silicon N-shaped layer, and it is as contact layer dorsad;
Use silver to form the metal electrode that a thickness is 2000A on contact layer dorsad in this, obtain solar cell of the present invention.The contrast figure of the power-voltage and current of solar cell of the present invention-voltage as shown in Figure 2.
3.2 the solar cell that uses prior art to prepare
As described in embodiment 3.1, the present embodiment makes solar cell via identical manufacture method haply, its difference is, this example in obtain one there is the AZO substrate of grain surface structure after, the AZO substrate that immediately this is had to the grain surface structure is cleaned;
Exist side by side and use PECVD, at the temperature of 200 ° of C, the AZO substrate that adopts the silane (H2+SiH4) of diluted in hydrogen and borine (B2H6) gas that adulterates to have the grain surface structure in this forms a uncrystalline silicon p-type layer,
The follow-up PECVD that sequentially uses forms a uncrystalline silicon intrinsic layer and uncrystalline silicon N-shaped layer on this uncrystalline silicon p-type layer, and step and technological parameter are identical with embodiment 3.1, at this, just repeat no more, and finally obtain the solar cell of prior art.The contrast figure of the power-voltage and current of the solar cell of prior art-voltage as shown in Figure 3.
3.3 the comparison of the solar cell of solar cell of the present invention and prior art
Each characterisitic parameter of the solar cell of solar cell of the present invention and prior art is as shown in table 2 below.
The character of the character of table 2 solar cell of the present invention and the solar cell of prior art
V: volt
MA: milliampere
MW: milliwatt
Ohm: ohm
By table 2, can be learnt, the solar cell of prior art all has similar characteristic to solar cell of the present invention in parameters such as open circuit voltage, short circuit current, peak power output, fill factor, curve factor, series resistance, parallel resistance and transfer ratios.
The invention has the advantages that, when manufacturing the p-Si/TCO substrate, flood this TCO substrate in using an acid solution, obtain one there is the TCO substrate of grain surface structure after, continue and utilize PVD that uncrystalline silicon p-type layer is deposited on this TCO substrate with grain surface structure, this uncrystalline silicon p-type layer is used as to a secluding film, in case the TCO film of stop bit under uncrystalline silicon p-type layer stored for a long time and oxidation, therefore this p-Si/TCO substrate can reach long term storage and the problem that increases without resistance, therefore avoided the problem of the substrate damage rate raising with transparent conductive oxide film of uncrystalline silicon, follow-up while again this p-Si/TCO substrate being transferred to the solar cell dealer, continue again and plate uncrystalline silicon intrinsic layer and uncrystalline silicon N-shaped layer with PECVD.The method neither increases the integrated artistic step and does not also increase extra charge, and it is similar to the uncrystalline silicon p-type layer character of using PECVD to manufacture to use PVD to manufacture its character of uncrystalline silicon p-type layer, and adopt the solar cell that the present invention makes to make and know that solar cell also possesses similar characteristic to art methods, expection the technology of the present invention can reduce costs widely and compare use in prior art and have the cost that the glass substrate of FTO film reduces by more than 50.
Claims (7)
1. a method for preparing the substrate with p-type uncrystalline silicon and transparent conductive oxide film, is characterized in that, the method that described preparation has the substrate of p-type uncrystalline silicon and transparent conductive oxide film comprises the following steps:
Complete one has the substrate of transparent conductive oxide film;
Form texture in the described surface with substrate of transparent conductive oxide film, obtain a substrate with transparent conductive oxide film with grain surface structure; And
Use physical vaporous deposition to form a uncrystalline silicon p-type layer on the described substrate with transparent conductive oxide film with grain surface structure, obtain a substrate that possesses p-type uncrystalline silicon and transparent conductive oxide film.
2. preparation as claimed in claim 1 has the method for the substrate of p-type uncrystalline silicon and transparent conductive oxide film, it is characterized in that, the complete described step with substrate of transparent conductive oxide film more comprises a first complete base material; Deposition one transparent conductive oxide film on described base material.
3. preparation as claimed in claim 1 has the method for the substrate of p-type uncrystalline silicon and transparent conductive oxide film, it is characterized in that, form texture in the described surface with substrate of transparent conductive oxide film, obtain a substrate with transparent conductive oxide film with grain surface structure, it is to use the described substrate with transparent conductive oxide film of an acid solution dipping.
4. preparation has the method for the substrate of p-type uncrystalline silicon and transparent conductive oxide film as claimed any one in claims 1 to 3, it is characterized in that, transparent conductive oxide film is the sull that contains zinc oxide.
5. preparation has the method for the substrate of p-type uncrystalline silicon and transparent conductive oxide film as claimed any one in claims 1 to 3, it is characterized in that, transparent conductive oxide film is the aluminum zinc oxide film.
6. preparation as claimed in claim 1 has the method for the substrate of p-type uncrystalline silicon and transparent conductive oxide film, it is characterized in that, described physical vaporous deposition is sputtering method, and the target used in the sputtering method polysilicon target that is doped with boron.
7. the substrate with p-type uncrystalline silicon and transparent conductive oxide film, is characterized in that, for the described method of any one in claim 1 to 6 makes.
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Citations (6)
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|---|---|---|---|---|
| CN101740358A (en) * | 2009-12-02 | 2010-06-16 | 中国科学院半导体研究所 | Method for preparing P type poly-silicon thin film on glass substrate |
| WO2010111197A2 (en) * | 2009-03-25 | 2010-09-30 | Intermolecular, Inc. | Acid chemistries and methodologies for texturing transparent conductive oxide materials |
| CN102270705A (en) * | 2011-08-05 | 2011-12-07 | 保定天威集团有限公司 | Method for preparing transparent conductive electrode with dual-structure texture surface |
| US20120012171A1 (en) * | 2010-07-16 | 2012-01-19 | Applied Materials, Inc. | Thin film solar fabrication process, deposition method for tco layer, and solar cell precursor layer stack |
| CN102339900A (en) * | 2010-07-16 | 2012-02-01 | 应用材料股份有限公司 | Thin-film solar fabrication process, deposition method for TCO layer, and solar cell precursor layer stack |
| US20120031479A1 (en) * | 2010-08-06 | 2012-02-09 | Applied Materials, Inc. | Thin film solar fabrication process, deposition method for tco layer, and solar cell precursor layer stack |
-
2012
- 2012-05-21 CN CN2012101578537A patent/CN103426974A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2010111197A2 (en) * | 2009-03-25 | 2010-09-30 | Intermolecular, Inc. | Acid chemistries and methodologies for texturing transparent conductive oxide materials |
| CN101740358A (en) * | 2009-12-02 | 2010-06-16 | 中国科学院半导体研究所 | Method for preparing P type poly-silicon thin film on glass substrate |
| US20120012171A1 (en) * | 2010-07-16 | 2012-01-19 | Applied Materials, Inc. | Thin film solar fabrication process, deposition method for tco layer, and solar cell precursor layer stack |
| CN102339900A (en) * | 2010-07-16 | 2012-02-01 | 应用材料股份有限公司 | Thin-film solar fabrication process, deposition method for TCO layer, and solar cell precursor layer stack |
| US20120031479A1 (en) * | 2010-08-06 | 2012-02-09 | Applied Materials, Inc. | Thin film solar fabrication process, deposition method for tco layer, and solar cell precursor layer stack |
| CN102270705A (en) * | 2011-08-05 | 2011-12-07 | 保定天威集团有限公司 | Method for preparing transparent conductive electrode with dual-structure texture surface |
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Application publication date: 20131204 |