CN105185861A - Glass-structure-based thin-film solar battery and preparation method thereof - Google Patents

Glass-structure-based thin-film solar battery and preparation method thereof Download PDF

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CN105185861A
CN105185861A CN201510476916.9A CN201510476916A CN105185861A CN 105185861 A CN105185861 A CN 105185861A CN 201510476916 A CN201510476916 A CN 201510476916A CN 105185861 A CN105185861 A CN 105185861A
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preparation
film
flow
quantum well
minutes
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陈志强
马明一
黄超
黄力
李嵩
殷绍睿
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Liaoning Henghua Navigation Electric Power Equipment Engineering Co Ltd
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Liaoning Henghua Navigation Electric Power Equipment Engineering Co Ltd
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    • H01L31/03048—Inorganic materials including, apart from doping materials or other impurities, only AIIIBV compounds including ternary or quaternary compounds, e.g. GaAlAs, InGaAs, InGaAsP comprising a nitride compounds, e.g. InGaN
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Abstract

The invention relates to a glass-structure-based thin-film solar battery and a preparation method thereof, wherein the band gap of the intrinsic layer of the battery can be adjusted and the battery has a quantum well structure. The battery comprises a metal Ag electrode, an ITO transparent conductive film, an N type InGaN film, a quantum well InxGa(1-x)N intrinsic layer with an adjustable band gap, a P type InGaN film, a GZO transparent conductive film, and a BCN insulating protective layer and a common glass substrate successively from top to bottom. The value of the x of the InxGa(1-x)N is from ) to 1. During the preparation process, the traditional Si solar battery material and structure are changed and the InxGa(1-x)N quantum well intrinsic crystal film with the adjustable band gap is used as the solar battery material; and because the InxGa(1-x)N material has advantages of high stability, good anti-corrosion performance, tunnel barrier, and low light loss coefficient, the conversion efficiency of the battery is improved. Besides, the GZO transparent conductive film is used as the transparent conductive electrode, so that the light transmittance of the thin-film solar battery is enhanced and the anti-corrosion performance of the transparent electrode is improved and thus the photoelectric conversion efficiency of the thin-film solar battery is substantially improved.

Description

A kind of glass structure thin-film solar cells and preparation method
Technical field
The invention belongs to a kind of glass substrate technical field of solar cell manufacturing, particularly a kind of intrinsic layer gap tunable and there is glass structure thin-film solar cells and the preparation method of quantum well structure.
Background technology
The material of preparing of traditional solar cell crystal silicon solar energy battery is divided into: monocrystalline silicon (sc-Si) and polysilicon (mc-Si).In the solar battery process of standard, usually boron is added in the melt of vertical pulling technique, thus produces p-type silicon chip, then mix N-shaped impurity, to form p-n junction.Monocrystalline silicon is the crystal structure of rule, and its each atom is arranged in the position foredoomed ideally, and therefore, the theory and technology of monocrystalline silicon promptly could be applied to crystalline material, shows measurable and uniform behavioral trait.As the material being used for preparing solar cell the earliest, the technology of preparing of monocrystaline silicon solar cell is the most ripe, and conversion efficiency is higher, is the leading role in market always.But because the manufacture process of single crystal silicon material must be extremely careful and slow, so be a kind of silicon materials the most expensive.Therefore the polysilicon that price is more cheap is used to manufacture solar cell, although be slightly poorer than monocrystalline qualitatively just fast widely.
The manufacturing process of polysilicon is so strict unlike monocrystalline silicon, because this reducing material preparation cost, becomes the focus competitively developed at present.But the existence of grain boundary produces more defect, hinders carrier mobility, and in forbidden band, create extra energy level, define effective spot and P-N junction short circuit to electronics and hole, thus battery performance reduces.In order to prevent serious grain boundary layer recombination losses, the crystallite dimension of polycrystalline silicon material necessarily requires at several mm in size, makes independent crystal grain extend to the back side from the front of battery, reduces the resistance of carrier mobility.This kind of polycrystalline silicon material has been widely used in the manufacture of commercial battery.The production cost reducing material is the key of reduction crystalline silicon photovoltaic product cost, and the main development direction of current crystal silicon solar energy battery is: high efficiency, low cost and sheet.
Thin film solar cell is owing to using material less, obvious minimizing is had compared with accumulation type solar cell with regard to the cost of each module, energy required on fabrication schedule also comparatively accumulation type solar cell come little, it also has the link block integrating pattern simultaneously, just can save standalone module thus required at the fixing cost be connected with inside.Future thin film type solar cell may replace now generally conventional silicon solar cell, and become the market mainstream.
Thin-film solar cells has the series of advantages such as lightweight, efficient, high-specific-power, consumptive material are few, can use as energy elements and structure member simultaneously.In thin-film solar cells preparation, photoelectric conversion material is deposited in different substrates, as glass, stainless steel foil or polymer etc.Therefore, solar cell requires that photoelectric conversion material has strong light absorption, and low temperature crystallization, cryogenic device make and stable material behavior etc., and be the important component part of relation battery conversion efficiency, be therefore the emphasis of solar cell developmental research always.
But traditional thin-film solar cells material all adopts Si as its PIN layer, and its band gap is fixed, unadjustable.
Summary of the invention
Technical problem to be solved by this invention is that providing a kind of adopts intrinsic layer gap tunable and have quantum well structure In xga 1-Xn, as its material, makes more sunlight enter battery surface, improves glass structure thin-film solar cells and the preparation method of its transformation efficiency.
The present invention is achieved in that
A kind of glass structure thin-film solar cells, this battery comprises the quantum well In of metal A g electrode, ITO transparent conductive film, N-type InGaN film, gap tunable from top to bottom successively xga 1-xn intrinsic layer, P type InGaN film, GZO transparent conductive film, BCN insulating protective layer and common glass substrate, wherein In xga 1-xin N, the value of x is 0 ~ 1.
A preparation method for glass structure thin-film solar cells, prepares the quantum well In of BCN insulating protective layer, GZO transparent conductive film, P type InGaN film, gap tunable successively at common glass substrate xga 1-xn intrinsic layer, N-type InGaN film, ITO transparent conductive film and metal A g electrode.
Further, common glass substrate prepares BCN insulating protective layer, and common glass substrate substrate first uses ionized water Ultrasonic Cleaning after 5 minutes, dries up send into magnetron sputtering reative cell, 8.0 × 10 with nitrogen -4under the condition of Pa vacuum; deposition preparation BCN insulating protective layer; its technological parameter condition is: nitrogen and methane are as mixed gas reaction source; its nitrogen methane flow compares 2:1; the purity of reactive sputtering boron target is 99.99%; underlayer temperature is 100 DEG C ~ 200 DEG C, and sedimentation time is 30 minutes to 1 hour.
Further, GZO base transparent conducting film is prepared; Its technological parameter condition is: adopt electron cyclotron resonance plasma to strengthen organic chemical vapor deposition system, trimethyl gallium and diethyl zinc and oxygen that argon gas carries is passed in reative cell, its flow-rate ratio is 1:2:80 ~ 1:3:90, depositing temperature is 200 DEG C ~ 400 DEG C, microwave power is 650W, deposition pressure is 0.8Pa ~ 1.2Pa, and sedimentation time is 10 minutes ~ 20 minutes.
Further, the adjustable PIN layer InxGa1-xN quantum well crystal film of band gap is prepared;
Its technological parameter condition is: in reative cell, pass into H 2the trimethyl gallium of dilution and trimethyl indium, according to concentration expressed in percentage by volume, wherein trimethyl gallium concentration 5% and trimethyl indium concentration 5%, H 2concentration is 95%, and the flow of its trimethyl gallium is 1 ~ 3sccm and trimethyl indium flow is 0.5 ~ 1.5sccm, and nitrogen flow is 80 ~ 120sccm, and doping adds H 2dilute two luxuriant magnesium, concentration of volume percent is 5%, and flow is 0.5-1sccm, and depositing temperature is 200 ~ 300 DEG C, and microwave power is 600 ~ 750W, and deposition pressure is 0.9 ~ 1.4Pa, and sedimentation time is 40 ~ 60 minutes preparation P layer In xga 1-xn quantum well crystal film, then continues to strengthen in organic chemical vapor deposition system at employing electron cyclotron resonance plasma to prepare the adjustable I layer In of band gap xga 1-xn quantum well intrinsic crystal film; Its technological parameter condition is: in reative cell, pass into H 2the trimethyl gallium of dilution and trimethyl indium, TMGa flow rate is the flow 2.5 ~ 4sccm of 2.0 ~ 3sccm and trimethyl indium, nitrogen flow is 80 ~ 120sccm, depositing temperature is 200 ~ 300 DEG C, microwave power is 650W, deposition pressure is 0.9 ~ 1.2Pa, and sedimentation time is 40 ~ 60 minutes preparation I layer In xga 1-xn quantum well crystal film; Finally continue to strengthen in organic chemical vapor deposition system at employing electron cyclotron resonance plasma to prepare the adjustable N layer In of band gap xga 1-xn quantum well crystal film; Its technological parameter condition is: in reative cell, pass into H 2the trimethyl gallium of dilution and trimethyl indium, TMGa flow rate is the flow 1.2 ~ 1.5sccm of 0.8 ~ 1sccm and trimethyl indium, nitrogen flow is 80 ~ 120sccm, depositing temperature is 300 ~ 400 DEG C, microwave power is 650W, deposition pressure is 0.8 ~ 1.2Pa, and sedimentation time is 40 ~ 60 minutes preparation N layer In xga 1-xn quantum well crystal film.
Further, ITO base transparent conducting film is prepared; Its technological parameter condition is: oxygen is as gas reaction source, and its oxygen flow is 10 ~ 20sccm, and the purity of reactive sputtering indium metal target is 99.99%, and underlayer temperature is 50 DEG C ~ 150 DEG C, and sedimentation time is 3 ~ 10 minutes.
Further, described preparation metal A g electrode, prepared by employing magnetron sputtering, its technological parameter condition is: argon gas is as gas reaction source, its argon flow amount is 10 ~ 20sccm, the purity of reactive sputtering silver metal target is 99.99%, and underlayer temperature is 50 DEG C ~ 150 DEG C, and sedimentation time is 3 ~ 10 minutes.
Compared with prior art, beneficial effect is in the present invention: the model that the present invention relates to the solar cell of one " Ag electrode/ITO transparent conductive film/PIN:InGaN/GZO transparent conductive film/BCN insulating protective layer/common glass substrate " structure.The present invention, in preparation process, changes traditional Si solar cell material and structure, introduces and has the adjustable In of band gap xga 1-xn quantum well intrinsic crystal film as solar cell material, In xga 1-xn material has to be stablized, corrosion-resistant and have tunneling barrier and low light loss coefficient, improves the transformation efficiency of battery.Next have employed GZO transparent membrane as transparency conductive electrode, and the light transmittance adding thin-film solar cells improves the decay resistance of transparency electrode simultaneously, and the photoelectric conversion efficiency of thin-film solar cells is greatly improved.Adopt BCN as insulating protective layer, further enhancing the useful life of thin-film solar cells.
Accompanying drawing explanation
Fig. 1 be thin-film solar cells of the present invention prepare structure chart;
Fig. 2 is the preparation flow figure of thin-film solar cells of the present invention;
Fig. 3 is the XRD collection of illustrative plates of solar cell of the present invention;
Atomic force microscope (AFM) collection of illustrative plates of Fig. 4 InxGa1-xN quantum well intrinsic crystal film.
Embodiment
In order to make object of the present invention, technical scheme and advantage clearly understand, below in conjunction with embodiment, the present invention is further elaborated.Should be appreciated that specific embodiment described herein only in order to explain the present invention, be not intended to limit the present invention.
The model of the XRD test adopted in the present invention is BrukerAXSD8, and x-ray source is the Cu-K α of λ=0.15418nm.
The model of the atomic force microscope (AFM) that the present invention utilizes is Picoscan2500, originates in Agilent company.Under the test condition of normal room temperature, testing and analyzing is carried out to the pattern of film sample.The test analysis region of sample is 2 μm × 2 μm.
Embodiment 1
See Fig. 1 composition graphs 2, (1), by common corning glass substrate base first use ionized water Ultrasonic Cleaning after 5 minutes, dry up with nitrogen and send into magnetron sputtering reative cell, 8.0 × 10 -4under the condition of Pa vacuum, deposition preparation BCN insulating barrier.Its technological parameter condition is: nitrogen and methane are as mixed gas reaction source, and its nitrogen methane flow is than 2:1, and the purity of reactive sputtering boron target is 99.99%, and underlayer temperature is 100 DEG C, and sedimentation time is 30 minutes.
(2), then GZO base transparent conducting film is prepared; Its technological parameter condition is: adopt electron cyclotron resonance plasma to strengthen organic chemical vapor deposition system (ECR-PEMOCVD), passes into trimethyl gallium (TMGa) and diethyl zinc (DEZn) and oxygen (O that argon gas (Ar) carries in reative cell 2), its flow-rate ratio is 1:3:90, and depositing temperature is 200 DEG C, and microwave power is 650W, and deposition pressure is 0.8Pa, and sedimentation time is 10 minutes.
(3), continue adopting electron cyclotron resonance plasma to strengthen the PIN layer In that in organic chemical vapor deposition system (ECR-PEMOCVD), preparation band gap is adjustable xga 1-xn quantum well crystal film; Its technological parameter condition is: in reative cell, pass into H 2the trimethyl gallium (TMGa) of dilution and trimethyl indium (TMIn), according to concentration expressed in percentage by volume, wherein trimethyl gallium concentration 5% and trimethyl indium concentration 5%, H 2concentration is 95%, and the flow of its trimethyl gallium is 3sccm and trimethyl indium flow is 1.5sccm, nitrogen (N 2) flow is 80sccm, doping adds H 2dilute two luxuriant magnesium, concentration of volume percent is 5%, and flow is 1sccm, and depositing temperature is 200 DEG C, and microwave power is 650W, and deposition pressure is 0.9Pa, and sedimentation time is 40 minutes preparation P layer In xga 1-xn quantum well crystal film.Then continue adopting electron cyclotron resonance plasma to strengthen the I layer In that in organic chemical vapor deposition system (ECR-PEMOCVD), preparation band gap is adjustable xga 1-xn quantum well intrinsic crystal film; Its technological parameter condition is: in reative cell, pass into H 2the trimethyl gallium (TMGa) of dilution and trimethyl indium (TMIn), TMGa flow rate is the flow 1sccm of 2.0sccm and trimethyl indium, nitrogen (N 2) flow is 90sccm, depositing temperature is 300 DEG C, and microwave power is 650W, and deposition pressure is 1.0Pa, and sedimentation time is 60 minutes preparation I layer In xga 1-xn quantum well crystal film.Finally continue adopting electron cyclotron resonance plasma to strengthen the N layer In that in organic chemical vapor deposition system (ECR-PEMOCVD), preparation band gap is adjustable xga 1-xn quantum well crystal film; Its technological parameter condition is: in reative cell, pass into H 2the trimethyl gallium (TMGa) of dilution and trimethyl indium (TMIn), TMGa flow rate is the flow 1.2sccm of 0.8sccm and trimethyl indium, nitrogen (N 2) flow is 90sccm, depositing temperature is 400 DEG C, and microwave power is 650W, and deposition pressure is 0.9Pa, and sedimentation time is 50 minutes preparation N layer In xga 1-xn quantum well crystal film.
(4) magnetron sputtering preparation preparation ITO base transparent conducting film, is adopted; Its technological parameter condition is: oxygen gas is as gas reaction source, and its oxygen flow is 10sccm, and the purity of reactive sputtering indium metal target is 99.99%, and underlayer temperature is 50 DEG C, and sedimentation time is 3 minutes.
(5), prepare metal A g electrode, adopt magnetron sputtering preparation, its technological parameter condition is: argon gas is as gas reaction source, its argon flow amount is 10sccm, the purity of reactive sputtering silver metal target is 99.99%, and underlayer temperature is 50 DEG C, and sedimentation time is 3 minutes.
Embodiment 2
(1), by common corning glass substrate base first use ionized water Ultrasonic Cleaning after 5 minutes, dry up with nitrogen and send into magnetron sputtering reative cell, 8.0 × 10 -4under the condition of Pa vacuum, deposition preparation BCN insulating barrier.Its technological parameter condition is: nitrogen and methane are as mixed gas reaction source, and its nitrogen methane flow is than 2:1, and the purity of reactive sputtering boron target is 99.99%, and underlayer temperature is 150 DEG C, and sedimentation time is 40 minutes.
(2), then GZO base transparent conducting film is prepared; Its technological parameter condition is: adopt electron cyclotron resonance plasma to strengthen organic chemical vapor deposition system (ECR-PEMOCVD), passes into trimethyl gallium (TMGa) and diethyl zinc (DEZn) and oxygen (O that argon gas (Ar) carries in reative cell 2), its flow-rate ratio is 1:2:80, and depositing temperature is 250 DEG C, and microwave power is 650W, and deposition pressure is 0.9Pa, and sedimentation time is 15 minutes.
(3), continue adopting electron cyclotron resonance plasma to strengthen the PIN layer In that in organic chemical vapor deposition system (ECR-PEMOCVD), preparation band gap is adjustable xga 1-xn quantum well crystal film; Its technological parameter condition is: in reative cell, pass into H 2the trimethyl gallium (TMGa) of dilution and trimethyl indium (TMIn), according to concentration expressed in percentage by volume, wherein trimethyl gallium concentration 5% and trimethyl indium concentration 5%, H 2concentration is 95%, and the flow of its trimethyl gallium is 1sccm and trimethyl indium flow is 0.5sccm, nitrogen (N 2) flow is 80sccm, doping adds H 2dilute two luxuriant magnesium, the concentration of volume percent of two luxuriant magnesium is 5%, and flow is 0.5sccm depositing temperature is 200 DEG C, and microwave power is 650W, and deposition pressure is 0.9Pa, and sedimentation time is 40 minutes preparation P layer In xga 1-xn quantum well crystal film.Then continue adopting electron cyclotron resonance plasma to strengthen the I layer In that in organic chemical vapor deposition system (ECR-PEMOCVD), preparation band gap is adjustable xga 1-xn quantum well intrinsic crystal film; Its technological parameter condition is: in reative cell, pass into H 2the trimethyl gallium (TMGa) of dilution and trimethyl indium (TMIn), TMGa flow rate is the flow 2.5sccm of 3sccm and trimethyl indium, nitrogen (N 2) flow is 90sccm, depositing temperature is 300 DEG C, and microwave power is 650W, and deposition pressure is 1.0Pa, and sedimentation time is 60 minutes preparation I layer In xga 1-xn quantum well crystal film.Finally continue adopting electron cyclotron resonance plasma to strengthen the N layer In that in organic chemical vapor deposition system (ECR-PEMOCVD), preparation band gap is adjustable xga 1-xn quantum well crystal film; Its technological parameter condition is: in reative cell, pass into H 2the trimethyl gallium (TMGa) of dilution and trimethyl indium (TMIn), TMGa flow rate is the flow 1.5sccm of 1sccm and trimethyl indium, nitrogen (N 2) flow is 90sccm, depositing temperature is 400 DEG C, and microwave power is 650W, and deposition pressure is 0.9Pa, and sedimentation time is 50 minutes preparation N layer In xga 1-xn quantum well crystal film.
(4) magnetron sputtering preparation preparation ITO base transparent conducting film, is adopted; Its technological parameter condition is: oxygen gas is as gas reaction source, and its oxygen flow is 18sccm, and the purity of reactive sputtering indium metal target is 99.99%, and underlayer temperature is 100 DEG C, and sedimentation time is 6 minutes.
(5), prepare metal A g electrode, adopt magnetron sputtering preparation, its technological parameter condition is: argon gas is as gas reaction source, its argon flow amount is 15sccm, the purity of reactive sputtering silver metal target is 99.99%, and underlayer temperature is 80 DEG C, and sedimentation time is 5 minutes.
Embodiment 3
(1), by common corning glass substrate base first use ionized water Ultrasonic Cleaning after 5 minutes, dry up with nitrogen and send into magnetron sputtering reative cell, 8.0 × 10 -4under the condition of Pa vacuum, deposition preparation BCN insulating barrier.Its technological parameter condition is: nitrogen and methane are as mixed gas reaction source, and its nitrogen methane flow is than 2:1, and the purity of reactive sputtering boron target is 99.99%, and underlayer temperature is 180 DEG C, and sedimentation time is 50 minutes.
(2), then GZO base transparent conducting film is prepared; Its technological parameter condition is: adopt electron cyclotron resonance plasma to strengthen organic chemical vapor deposition system (ECR-PEMOCVD), passes into trimethyl gallium (TMGa) and diethyl zinc (DEZn) and oxygen (O that argon gas (Ar) carries in reative cell 2), its flow-rate ratio is 1:3:90, and depositing temperature is 300 DEG C, and microwave power is 650W, and deposition pressure is 1.1Pa, and sedimentation time is 17 minutes.
(3), continue adopting electron cyclotron resonance plasma to strengthen the PIN layer In that in organic chemical vapor deposition system (ECR-PEMOCVD), preparation band gap is adjustable xga 1-xn quantum well crystal film; Its technological parameter condition is: in reative cell, pass into H 2the trimethyl gallium (TMGa) of dilution and trimethyl indium (TMIn), according to concentration expressed in percentage by volume, wherein trimethyl gallium concentration 5% and trimethyl indium concentration 5%, H 2concentration is 95%, and the flow of its trimethyl gallium is 2sccm and trimethyl indium flow is 1sccm, nitrogen (N 2) flow is 80sccm, doping adds H 2dilute two luxuriant magnesium, concentration of volume percent is 5%, and flow is 0.5sccm, and depositing temperature is 200 DEG C, and microwave power is 650W, and deposition pressure is 0.9Pa, and sedimentation time is 40 minutes preparation P layer In xga 1-xn quantum well crystal film.Then continue adopting electron cyclotron resonance plasma to strengthen the I layer In that in organic chemical vapor deposition system (ECR-PEMOCVD), preparation band gap is adjustable xga 1-xn quantum well intrinsic crystal film; Its technological parameter condition is: in reative cell, pass into H 2the trimethyl gallium (TMGa) of dilution and trimethyl indium (TMIn), TMGa flow rate is the flow 2.5sccm of 3sccm and trimethyl indium, nitrogen (N 2) flow is 120sccm, depositing temperature is 300 DEG C, and microwave power is 650W, and deposition pressure is 1.2Pa, and sedimentation time is 60 minutes preparation I layer In xga 1-xn quantum well crystal film.Finally continue adopting electron cyclotron resonance plasma to strengthen the N layer In that in organic chemical vapor deposition system (ECR-PEMOCVD), preparation band gap is adjustable xga 1-xn quantum well crystal film; Its technological parameter condition is: in reative cell, pass into H 2the trimethyl gallium (TMGa) of dilution and trimethyl indium (TMIn), TMGa flow rate is the flow 1.2sccm of 0.8sccm and trimethyl indium, nitrogen (N 2) flow is 100sccm, depositing temperature is 400 DEG C, and microwave power is 650W, and deposition pressure is 0.9Pa, and sedimentation time is 50 minutes preparation N layer In xga 1-xn quantum well crystal film.
(4) magnetron sputtering preparation preparation ITO base transparent conducting film, is adopted; Its technological parameter condition is: oxygen gas is as gas reaction source, and its oxygen flow is 20sccm, and the purity of reactive sputtering indium metal target is 99.99%, and underlayer temperature is 130 DEG C, and sedimentation time is 9 minutes.
(5), prepare metal A g electrode, adopt magnetron sputtering preparation, its technological parameter condition is: argon gas is as gas reaction source, its argon flow amount is 16sccm, the purity of reactive sputtering silver metal target is 99.99%, and underlayer temperature is 120 DEG C, and sedimentation time is 5 minutes.
Embodiment 4
(1), by common corning glass substrate base first use ionized water Ultrasonic Cleaning after 5 minutes, dry up with nitrogen and send into magnetron sputtering reative cell, 8.0 × 10 -4under the condition of Pa vacuum, deposition preparation BCN insulating barrier.Its technological parameter condition is: nitrogen and methane are as mixed gas reaction source, and its nitrogen methane flow is than 2:1, and the purity of reactive sputtering boron target is 99.99%, and underlayer temperature is 190 DEG C, and sedimentation time is 45 minutes.
(2), then GZO base transparent conducting film is prepared; Its technological parameter condition is: adopt electron cyclotron resonance plasma to strengthen organic chemical vapor deposition system (ECR-PEMOCVD), passes into trimethyl gallium (TMGa) and diethyl zinc (DEZn) and oxygen (O that argon gas (Ar) carries in reative cell 2), its flow-rate ratio is 1:3:90, and depositing temperature is 350 DEG C, and microwave power is 650W, and deposition pressure is 1.0Pa, and sedimentation time is 16 minutes.
(3), continue adopting electron cyclotron resonance plasma to strengthen the PIN layer In that in organic chemical vapor deposition system (ECR-PEMOCVD), preparation band gap is adjustable xga 1-xn quantum well crystal film; Its technological parameter condition is: in reative cell, pass into H 2the trimethyl gallium (TMGa) of dilution and trimethyl indium (TMIn), H 2the trimethyl gallium of dilution and trimethyl indium, according to concentration expressed in percentage by volume, wherein trimethyl gallium concentration 5% and trimethyl indium concentration 5%, H 2concentration is 95%, and the flow of its trimethyl gallium is 2sccm and trimethyl indium flow is 1.5sccm, and nitrogen flow is 110sccm, and doping adds H 2dilute two luxuriant magnesium, concentration of volume percent is 5%, and flow is 0.5-1sccm, and depositing temperature is 200 DEG C, and microwave power is 650W, and deposition pressure is 1.4Pa, and sedimentation time is 40 minutes preparation P layer In xga 1-xn quantum well crystal film.Then continue adopting electron cyclotron resonance plasma to strengthen the I layer In that in organic chemical vapor deposition system (ECR-PEMOCVD), preparation band gap is adjustable xga 1-xn quantum well intrinsic crystal film; Its technological parameter condition is: in reative cell, pass into H 2the trimethyl gallium (TMGa) of dilution and trimethyl indium (TMIn), TMGa flow rate is the flow 2.5sccm of 2.0sccm and trimethyl indium, nitrogen (N 2) flow is 110sccm, depositing temperature is 250 DEG C, and microwave power is 650W, and deposition pressure is 1.0Pa, and sedimentation time is 60 minutes preparation I layer In xga 1-xn quantum well crystal film.Finally continue adopting electron cyclotron resonance plasma to strengthen the N layer In that in organic chemical vapor deposition system (ECR-PEMOCVD), preparation band gap is adjustable xga 1-xn quantum well crystal film; Its technological parameter condition is: in reative cell, pass into H 2the trimethyl gallium (TMGa) of dilution and trimethyl indium (TMIn), TMGa flow rate is the flow 1.2sccm of 0.8sccm and trimethyl indium, nitrogen (N 2) flow is 90sccm, depositing temperature is 400 DEG C, and microwave power is 650W, and deposition pressure is 1.2Pa, and sedimentation time is 50 minutes preparation N layer In xga 1-xn quantum well crystal film.
(4) magnetron sputtering preparation preparation ITO base transparent conducting film, is adopted; Its technological parameter condition is: oxygen is as gas reaction source, and its oxygen flow is 12sccm, and the purity of reactive sputtering indium metal target is 99.99%, and underlayer temperature is 80 DEG C, and sedimentation time is 9 minutes.
(5), prepare metal A g electrode, adopt magnetron sputtering preparation, its technological parameter condition is: argon gas is as gas reaction source, its argon flow amount is 20sccm, the purity of reactive sputtering silver metal target is 99.99%, and underlayer temperature is 100 DEG C, and sedimentation time is 8 minutes.
Embodiment 5
(1), by common corning glass substrate base first use ionized water Ultrasonic Cleaning after 5 minutes, dry up with nitrogen and send into magnetron sputtering reative cell, 8.0 × 10 -4under the condition of Pa vacuum, deposition preparation BCN insulating barrier.Its technological parameter condition is: nitrogen and methane are as mixed gas reaction source, and its nitrogen methane flow is than 2:1, and the purity of reactive sputtering boron target is 99.99%, and underlayer temperature is 200 DEG C, and sedimentation time is 1 hour.
(2), then GZO base transparent conducting film is prepared; Its technological parameter condition is: adopt electron cyclotron resonance plasma to strengthen organic chemical vapor deposition system (ECR-PEMOCVD), passes into trimethyl gallium (TMGa) and diethyl zinc (DEZn) and oxygen (O that argon gas (Ar) carries in reative cell 2), its flow-rate ratio is 1:2:80, and depositing temperature is 400 DEG C, and microwave power is 650W, and deposition pressure is 1.2Pa, and sedimentation time is 20 minutes.
(3), continue adopting electron cyclotron resonance plasma to strengthen the PIN layer In that in organic chemical vapor deposition system (ECR-PEMOCVD), preparation band gap is adjustable xga 1-xn quantum well crystal film; Its technological parameter condition is: in reative cell, pass into H 2the trimethyl gallium (TMGa) of dilution and trimethyl indium (TMIn), according to concentration expressed in percentage by volume, wherein trimethyl gallium concentration 5% and trimethyl indium concentration 5%, H 2concentration is 95%, and the flow of its trimethyl gallium is 2sccm and trimethyl indium flow is 1.5sccm, and nitrogen flow is 80sccm, and doping adds H 2dilute two luxuriant magnesium, concentration of volume percent is 5%, and flow is 1sccm, and depositing temperature is 200 DEG C, and microwave power is 650W, and deposition pressure is 0.9Pa, and sedimentation time is 40 minutes preparation P layer In xga 1-xn quantum well crystal film.Then continue adopting electron cyclotron resonance plasma to strengthen the I layer In that in organic chemical vapor deposition system (ECR-PEMOCVD), preparation band gap is adjustable xga 1-xn quantum well intrinsic crystal film; Its technological parameter condition is: in reative cell, pass into H 2the trimethyl gallium (TMGa) of dilution and trimethyl indium (TMIn), TMGa flow rate is the flow 2.5 ~ 4sccm of 2.0 ~ 3sccm and trimethyl indium, nitrogen (N 2) flow is 90sccm, depositing temperature is 300 DEG C, and microwave power is 650W, and deposition pressure is 1.0Pa, and sedimentation time is 60 minutes preparation I layer In xga 1-xn quantum well crystal film.Finally continue adopting electron cyclotron resonance plasma to strengthen the N layer In that in organic chemical vapor deposition system (ECR-PEMOCVD), preparation band gap is adjustable xga 1-xn quantum well crystal film; Its technological parameter condition is: in reative cell, pass into H 2the trimethyl gallium (TMGa) of dilution and trimethyl indium (TMIn), TMGa flow rate is the flow 1.5sccm of 0.8sccm and trimethyl indium, nitrogen (N 2) flow is 90sccm, depositing temperature is 400 DEG C, and microwave power is 650W, and deposition pressure is 0.9Pa, and sedimentation time is 50 minutes preparation N layer In xga 1-xn quantum well crystal film.
(4) magnetron sputtering preparation preparation ITO base transparent conducting film, is adopted; Its technological parameter condition is: oxygen gas is as gas reaction source, and its oxygen flow is 20sccm, and the purity of reactive sputtering indium metal target is 99.99%, and underlayer temperature is 150 DEG C, and sedimentation time is 10 minutes.
(5), prepare metal A g electrode, adopt magnetron sputtering preparation, its technological parameter condition is: argon gas is as gas reaction source, its argon flow amount is 20sccm, the purity of reactive sputtering silver metal target is 99.99%, and underlayer temperature is 150 DEG C, and sedimentation time is 10 minutes.
Experiment terminates the PIN type In of rear employing XRD analysis equipment to deposition preparation xga 1-xthe performance of N quantum well crystal film has carried out test analysis.Its result as shown in Figure 3, In as seen from Figure 3 xga 1-xn quantum well crystal film has excellent preferred orientation, illustrates that organization structure of film is more satisfactory.Continue to adopt atomic force microscope (AFM) to In xga 1-xthe pattern of N quantum well crystal film has carried out test analysis.Its result as shown in Figure 4, In as seen from Figure 4 xga 1-xn quantum well crystal film pattern is very smooth, and crystal grain distribution is very even.
The foregoing is only preferred embodiment of the present invention, not in order to limit the present invention, all any amendments done within the spirit and principles in the present invention, equivalent replacement and improvement etc., all should be included within protection scope of the present invention.

Claims (7)

1. a glass structure thin-film solar cells, is characterized in that, this battery comprises the quantum well In of metal A g electrode, ITO transparent conductive film, N-type InGaN film, gap tunable from top to bottom successively xga 1-xn intrinsic layer, P type InGaN film, GZO transparent conductive film, BCN insulating protective layer and common glass substrate, wherein In xga 1-xin N, the value of x is 0 ~ 1.
2. a preparation method for glass structure thin-film solar cells, is characterized in that, prepares the quantum well In of BCN insulating protective layer, GZO transparent conductive film, P type InGaN film, gap tunable at common glass substrate successively xga 1-xn intrinsic layer, N-type InGaN film, ITO transparent conductive film and metal A g electrode.
3. the preparation method of glass structure thin-film solar cells as claimed in claim 2; it is characterized in that, common glass substrate prepares BCN insulating protective layer, and common glass substrate substrate first uses ionized water Ultrasonic Cleaning after 5 minutes; dry up with nitrogen and send into magnetron sputtering reative cell, 8.0 × 10 -4under the condition of Pa vacuum; deposition preparation BCN insulating protective layer; its technological parameter condition is: nitrogen and methane are as mixed gas reaction source; its nitrogen methane flow compares 2:1; the purity of reactive sputtering boron target is 99.99%; underlayer temperature is 100 DEG C ~ 200 DEG C, and sedimentation time is 30 minutes to 1 hour.
4. the preparation method of glass structure thin-film solar cells according to claim 2, is characterized in that, preparation GZO base transparent conducting film; Its technological parameter condition is: adopt electron cyclotron resonance plasma to strengthen organic chemical vapor deposition system, trimethyl gallium and diethyl zinc and oxygen that argon gas carries is passed in reative cell, its flow-rate ratio is 1:2:80 ~ 1:3:90, depositing temperature is 200 DEG C ~ 400 DEG C, microwave power is 650W, deposition pressure is 0.8Pa ~ 1.2Pa, and sedimentation time is 10 minutes ~ 20 minutes.
5. the preparation method of glass structure thin-film solar cells according to claim 2, is characterized in that, the PIN layer InxGa1-xN quantum well crystal film that preparation band gap is adjustable;
Its technological parameter condition is: in reative cell, pass into H 2the trimethyl gallium of dilution and trimethyl indium, according to concentration expressed in percentage by volume, wherein trimethyl gallium concentration 5% and trimethyl indium concentration 5%, H 2concentration is 95%, and the flow of its trimethyl gallium is 1 ~ 3sccm and trimethyl indium flow is 0.5 ~ 1.5sccm, and nitrogen flow is 80 ~ 120sccm, and doping adds H 2dilute two luxuriant magnesium, concentration of volume percent is 5%, and flow is 0.5-1sccm, and depositing temperature is 200 ~ 300 DEG C, and microwave power is 600 ~ 750W, and deposition pressure is 0.9 ~ 1.4Pa, and sedimentation time is 40 ~ 60 minutes preparation P layer In xga 1-xn quantum well crystal film, then continues to strengthen in organic chemical vapor deposition system at employing electron cyclotron resonance plasma to prepare the adjustable I layer In of band gap xga 1-xn quantum well intrinsic crystal film; Its technological parameter condition is: in reative cell, pass into H 2the trimethyl gallium of dilution and trimethyl indium, TMGa flow rate is the flow 2.5 ~ 4sccm of 2.0 ~ 3sccm and trimethyl indium, nitrogen flow is 80 ~ 120sccm, depositing temperature is 200 ~ 300 DEG C, microwave power is 650W, deposition pressure is 0.9 ~ 1.2Pa, and sedimentation time is 40 ~ 60 minutes preparation I layer In xga 1-xn quantum well crystal film; Finally continue to strengthen in organic chemical vapor deposition system at employing electron cyclotron resonance plasma to prepare the adjustable N layer In of band gap xga 1-xn quantum well crystal film; Its technological parameter condition is: in reative cell, pass into H 2the trimethyl gallium of dilution and trimethyl indium, TMGa flow rate is the flow 1.2 ~ 1.5sccm of 0.8 ~ 1sccm and trimethyl indium, nitrogen flow is 80 ~ 120sccm, depositing temperature is 300 ~ 400 DEG C, microwave power is 650W, deposition pressure is 0.8 ~ 1.2Pa, and sedimentation time is 40 ~ 60 minutes preparation N layer In xga 1-xn quantum well crystal film.
6. the preparation method of glass structure thin-film solar cells according to claim 2, is characterized in that, preparation ITO base transparent conducting film; Its technological parameter condition is: oxygen is as gas reaction source, and its oxygen flow is 10 ~ 20sccm, and the purity of reactive sputtering indium metal target is 99.99%, and underlayer temperature is 50 DEG C ~ 150 DEG C, and sedimentation time is 3 ~ 10 minutes.
7. the preparation method of glass structure thin-film solar cells according to claim 2, it is characterized in that, described preparation metal A g electrode, prepared by employing magnetron sputtering, its technological parameter condition is: argon gas is as gas reaction source, and its argon flow amount is 10 ~ 20sccm, and the purity of reactive sputtering silver metal target is 99.99%, underlayer temperature is 50 DEG C ~ 150 DEG C, and sedimentation time is 3 ~ 10 minutes.
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