CN108550644B - Half lamination flexible silicon-based thin film solar battery of one kind and preparation method thereof - Google Patents
Half lamination flexible silicon-based thin film solar battery of one kind and preparation method thereof Download PDFInfo
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- H01L31/04—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices
- H01L31/042—PV modules or arrays of single PV cells
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Abstract
Half lamination flexible silicon-based thin film solar battery of one kind and preparation method thereof, belongs to silicon-based film solar cells field.The structure of the half lamination flexible silicon-based thin film solar battery includes sequentially connected preceding electrode, absorber and back electrode；Wherein, absorber PI1N1I2N2Half lamination absorber of structure, P are P-type non-crystalline silicon layer, I1For intrinsic amorphous silicon layer, N1For N1Type amorphous silicon layer, I2For intrinsic microcrystalline silicon layer, N2For N2Type amorphous silicon layer；Preparation method is to handle substrate layer to be sequentially depositing each layer using radio-frequency magnetron sputter method according to structure.The half lamination flexible silicon-based thin film solar battery uses half lamination PI1N1I2N2Structure effectively avoids the heavy doping problem of tunnel junctions in traditional laminated cell.On the basis of thinned laminated cell thickness, built in field intensity, short circuit current and the transformation efficiency of battery is can be improved in half laminated construction.The magnetically controlled sputter method of use, deposition process is efficient, cleans, is easily controllable.
Description
Technical field
The present invention relates to silicon-based film solar cells technical fields, specifically design a kind of half lamination flexible silicon base
Thin-film solar cells and preparation method thereof.
Background technique
It is increasingly depleted with economic continuous development and the energy, the energy have become influence social progress it is important because
Element.Solar cell is the main tool of Solar use, therefore the solar cell of developing low-cost, high-photoelectric transformation efficiency is
The matter of utmost importance faced as photovoltaic interface.Flexible amorphous silicon thin-film solar cell have be simple to manufacture, be at low cost, is flexible, light
Good electrical property, continuous large-area production, realize Photovoltaic Building Integration the advantages that, shortcoming be its there are light-induced degradation effects
It answers.For in the a-Si:H/ μ c-Si:H stacked solar cell, cascade solar cell of traditional unijunction PIN amorphous silicon film solar battery and PINPIN
The heavy doping problem of tunnel junctions in the Staebler-Wronski effect and laminate PIN PIN battery of amorphous silicon, proposition design a kind of half lamination
The novel silicon base thin-film solar cell structure of PININ structure.
The best light absorption design of solar battery structure needs to maximize the absorption of intrinsic layer and minimizes other layers
It absorbs, and such design method requires sufficient light trapping structure.The effect of light trapping structure is to be added to firing area in face of light
Scattering process so that more light is injected into battery, while partially can not will be inhaled as the back electrode of anti-reflection structure
The light of receipts is reflected back inside battery and forms light trapping to increase the transfer efficiency of battery.
In non-crystal silicon solar cell, diffusion length of the carrier in intrinsic layer is shorter, causes carrier not up to
Battery the two poles of the earth be collected before just by it is compound fall.In addition to this, there are more serious for traditional unijunction PIN type amorphous silicon film battery
Staebler-Wronski effect, and amorphous silicon is insensitive to the absorption of solar spectrum medium-long wave band, can only absorbing wavelength be 380nm-700nm
The sunlight of left and right.Therefore a kind of silicon-base thin-film battery of graded bandgap is designed to guarantee to make full use of solar spectrum.
It due to there is the n-p junction opposite with p-n junction, i.e., is logical inside multijunction cell in traditional laminate PIN PIN battery
The n-layer and p-type layer of two neighboring diode are crossed, forms what tunnel junctions interconnected, the built-in electricity of such p-n junction
Built in field direction inside field direction and diode is always opposite, it is always at reverse bias in the operating condition, but
Actually it does not form space-charge region, but forms short-circuit knot, if thinking, the electric conductivity of p-n junction is good and is unlikely to produce
Obvious resistance is given birth to it is necessary to make the n-p junction of laminated cell realize heavy doping.Theoretically, in high-concentration dopant, in amorphous silicon
A large amount of dangling bonds can be generated, the carrier to come from doped layer side is easy to be captured by these defect states, captured load
Stream is also accessible to the other side of doped layer by tunnel process, and the electronics of n-type area conduction band will soon be on interface and p
The hole-recombination of type area valence band, this recombination current become p-n junction to good conductivity without generating obvious resistance.And
The realization of heavy doping is always a bottleneck for restricting laminated cell development in silicon target.
Chinese patent CN201210529409.3 discloses a kind of p-i-n type thin-film solar cells, using substrate-electrode
- p-i-n layers-stressor layers-anti-reflecting layer-electrode layer structure of layer, feature are that the second doping type amorphous silicon layer surface forms stress
The mobility of electronics in the n-layer can be improved in layer, reduces light induced electron during n-layer is drifted about to the second electrode lay
By compound probability, the electron amount reached at the second electrode lay is improved.It is p-i-n type that the solar battery, which uses, is deposited
In more serious Staebler-Wronski effect.
Chinese patent CN102694049.A discloses a kind of efficient silicon thin film battery knot with novel interlayer structure
Structure, using amorphous silicon top battery/middle layer N-shaped crystallite silica/middle layer N-shaped microcrystal silicon/middle layer N-shaped crystallite silica/
Microcrystal silicon bottom battery structure is amorphous silicon/microcrystalline silicon tandem battery, it is characterized in that may remain in amorphous silicon/microcrystalline silicon tandem
While the top battery intrinsic layer thickness of battery is constant, the short-circuit current density and incident photon-to-electron conversion efficiency of battery are improved；The disadvantage is that
Battery structure involved in the patent is still traditional PINRPIN laminated cell, not can avoid laminated cell reverse p-n junctions institute
The heavy doping problem of the tunnel junctions of formation.
Chinese patent CN201220678505.X discloses a kind of amorphous silicon thin-film solar cell, uses anti-reflecting layer
Structure increases the impingement rate of light, but using plasma enhancing chemical vapour deposition technique manufactures silica-base film, this method pair
Environmental pollution is serious, and lacks the light trapping structure being made of electrode layer and back reflection layer.
Chinese patent CN105280736.A discloses a kind of amorphous silicon germanium thin film solar energy of two layer interface band gap buffer layer
Battery, it is characterised in that the method combined by the absorbed layer of band gap consecutive variations with i-p bilayer band gap buffer layer, with effective
The recombination probability of carrier is reduced, while surface treatment is carried out to back reflector and forms micro-nano structure, to effectively increase light
Transmission range in battery, and then increase light absorption, finally obtain efficient amorphous silicon germanium thin film battery.The battery lacks
Point is the doping that Ge element in film is realized using chemical vapor deposition method, and doping concentration is not easy to control.
Summary of the invention
The present invention for the problems of above-mentioned, propose a kind of half lamination flexible silicon-based thin film solar battery and its
Preparation method, the half lamination flexible silicon-based thin film solar battery are half laminated cell of silicon substrate, and half lamination absorber is using half
Lamination PI1N1I2N2Structure effectively avoids the heavy doping problem of tunnel junctions in traditional laminated cell.
The built in field of battery can be improved by half laminated construction on the basis of thinned laminated cell thickness by the present invention
Intensity, short circuit current and transformation efficiency.Preparation method uses magnetically controlled sputter method, and entire deposition process is efficient, cleans, is easy to control
System.
Half lamination flexible silicon-based thin film solar battery of one kind of the invention, structure include sequentially connected preceding electrode,
Absorber and back electrode；
The absorber is half lamination absorber, is half lamination PI1N1I2N2Structure, wherein P layers are P-type non-crystalline silicon
Layer, I1Layer is intrinsic amorphous silicon layer, N1Layer is N1Type amorphous silicon layer, I2Layer is intrinsic microcrystalline silicon layer, N2Layer is N2Type amorphous silicon layer；
N1Doping concentration be (1~5) × e16cm-3, N2Doping concentration be (1~5) × e19cm-3。
The half lamination absorber is the silica-base film material that amorphous silicon and microcrystalline silicon materials combine, is plural layers
Cascaded structure, the cascaded structure be realized after the completion of every layer of film deposition it is concatenated.
The half lamination flexible silicon-based thin film solar battery, structure further include substrate layer, buffer layer and sunken photosphere；
Wherein, whether transparent according to substrate layer, be divided into two kinds of connection types: when substrate layer is hyaline layer, half lamination flexible silicon base is thin
The structure of film solar cell be sequentially connected transparent substrate, preceding electrode, buffer layer, half lamination absorber, fall into photosphere and
Back electrode；When substrate layer is non transparent layer, before the structure of half lamination flexible silicon-based thin film solar battery is sequentially connected
Electrode, falls into photosphere, half lamination absorber, back electrode and nontransparent substrate layer at buffer layer, and according to light source direction, half lamination
Absorber is PI1N1I2N2Sequential organization.
The sunken photosphere is the multilayer light trapping structure comprising multilayer material, wherein closer to half lamination absorber, multilayer
The layer material refractive index of light trapping structure is bigger, multilayer light trapping structure close to half lamination absorber layer material refractive index≤
The refractive index of half lamination absorber, the number of plies >=2 layer of multilayer material.
Preferably, every layer material refractive index of the multilayer light trapping structure is 1.2-2.7.
The multilayer light trapping structure, layer material are preferably SiC layer, ZnO layer and SiO2Layer, SiC layer, ZnO layer and SiO2
Layer is arranged successively by the bigger sequence closer to half lamination absorber of refractive index；
Wherein, the refractive index that the refractive index of SiC is 2.7, ZnO is 2, SiO2Refractive index be 1.5, i.e., with from absorber by
It is proximal and distal, respectively SiC layer, ZnO layer and SiO2Layer.
Preferably, when the substrate layer is hyaline layer, preferably flexible and transparent PET or flexible and transparent PI；Described
When substrate layer is non transparent layer, preferably stainless steel plate.
Preferably, the preceding electrode is AZO transparent front electrode；
Preferably, the buffer layer is AZO homogeneous buffer layer or the heterogeneous buffer layer of AZO；When for AZO homogeneous buffer layer
When, buffer layer is AZO layers, when buffer layer heterogeneous for AZO, buffer layer Al2O3Buffer layer, Ag buffer layer, Al buffer layer or
One of ITO buffer layer；
Preferably, the back electrode is in AZO back reflector, golden back electrode, silver-colored back electrode or aluminum back electrode
It is a kind of.
The structure of the half lamination flexible silicon-based thin film solar battery are as follows: half lamination flexible silicon-based thin film solar-electricity
Pond is using flexible PET plastic as substrate layer, is upwards in turn Al using AZO as transparent front electrode2O3Buffer layer, half lamination absorb
Body, multilayer light trapping structure (SiC, ZnO, SiO2), back electrode AZO, specifically:
PET/AZO/Al2O3/P/I1/N1/I2/N2/SiC/ZnO/SiO2/AZO。
Overall thickness≤10 μm of the half lamination flexible silicon-based thin film solar battery, the film number of plies are 7~20 layers；
The substrate layer with a thickness of 0.001~0.250mm；
The preceding electrode with a thickness of 30~50nm；
The buffer layer with a thickness of 10~20nm；
200~600nm of the thickness of the back electrode；
The overall thickness of the half lamination absorber be 1.35 μm -2.55 μm, wherein P-type non-crystalline silicon layer with a thickness of 10
~30nm, intrinsic amorphous silicon layer is with a thickness of 300~400nm, N1Type amorphous silicon layer is with a thickness of 20~30nm, intrinsic micro crystal silicon thickness
Degree is 1000nm~2000nm, N2Type amorphous silicon layer is with a thickness of 20~45nm；
The multilayer light trapping structure, SiO2Layer with a thickness of 50~80nm, ZnO layer with a thickness of 30~50nm, SiC layer
With a thickness of 30~50nm.
The half lamination flexible silicon-based thin film solar battery, short circuit current is up to 18.24~22.57mA/cm2, half
The stable conversion efficiency of lamination flexible silicon-based thin film solar battery is up to 14.25%~17.36%.
The preparation method of half lamination flexible silicon-based thin film solar battery of one kind of the invention, comprising the following steps:
Step 1: processing substrate layer, the substrate layer that obtains that treated；
Step 2: radio-frequency magnetron sputter method is used on substrate layer, according to half lamination flexible silicon-based thin film solar battery
Structure is sequentially depositing each layer, obtains half lamination flexible silicon-based thin film solar battery；Wherein, each layer includes preceding electrode,
Buffer layer, P-type non-crystalline silicon layer, intrinsic amorphous silicon layer, N1Type amorphous silicon layer, intrinsic microcrystalline silicon layer, N2Type amorphous silicon layer, multilayer are fallen into
Photo structure and back electrode.
Its specific preparation method is broadly divided into following several:
(1) when substrate layer is transparent substrate, half lamination flexible silicon-based thin film solar battery of one kind of the invention
Preparation method, comprising the following steps:
Step 1: processing transparent substrate, the transparent substrate that obtains that treated；
Step 2: electrode before being sequentially depositing on transparent substrate using radio-frequency magnetron sputter method, buffer layer, P-type non-crystalline silicon
Layer, intrinsic amorphous silicon layer, N1Type amorphous silicon layer, intrinsic microcrystalline silicon layer, N2Type amorphous silicon layer falls into photosphere and back electrode, obtains half lap
Layer flexible silicon-based thin film solar battery.
In the step 2, the sunken photosphere uses wet etching making herbs into wool, guarantees electrode surface recess uniformity,
And the transverse width that is recessed is 1~4 μm.
(2) when the sunken photosphere is multilayer light trapping structure, the preparation of half lamination flexible silicon-based thin film solar battery
Method, comprising the following steps:
Step 1: processing substrate layer, the substrate layer that obtains that treated；
Step 2: electrode before being sequentially depositing on substrate layer using radio-frequency magnetron sputter method, buffer layer, P-type non-crystalline silicon layer,
Intrinsic amorphous silicon layer, N1Type amorphous silicon layer, intrinsic microcrystalline silicon layer, N2Type amorphous silicon layer, be followed successively by refractive index be sequentially reduced it is more
Layer light trapping structure and back electrode, obtain half lamination flexible silicon-based thin film solar battery.
In the step 2, the radio-frequency magnetron sputter method, in Ar and H2It is deposited in mixed-gas environment, wherein Ar
With H2Flow proportional be (30~40) sccm:(20~30) sccm.
(3) when substrate layer is nontransparent substrate layer, half lamination flexible silicon-based thin film solar battery of one kind of the invention
Preparation method, comprising the following steps:
Step 1: handling nontransparent substrate layer, the nontransparent substrate layer that obtains that treated；
Step 2: back electrode, N being sequentially depositing using radio-frequency magnetron sputter method on nontransparent substrate layer2Type amorphous silicon layer,
Intrinsic microcrystalline silicon layer, N1Type amorphous silicon layer, intrinsic amorphous silicon layer, P-type non-crystalline silicon layer, be followed successively by refractive index be sequentially reduced it is more
Layer light trapping structure, buffer layer and preceding electrode, obtain half lamination flexible silicon-based thin film solar battery.
For the N in half lamination absorber of battery1Layer, doping concentration ratio N2Layer is low, is expanded in the battery by carrier
It dissipates and forms gradual change electric field, therefore, N1Layer is both the N layer of sub- battery 1 and the P layer of sub- battery 2, is served both functions.It can be real
The recycling of existing sub- battery, avoids the heavy doping problem of traditional laminated cell tunnel composite junction.To realize this function, this
Patent realizes the gradual change of battery potential barrier using doping concentration and the difference of optical band gap, to form battery cascade.Cause
For P1Layer and P2Layer and N1Layer and N2Layer doping concentration is different, and reduces towards the direction of knot, and carrier is primarily generated at intrinsic
The area floor I, the N of novel half laminated cell1Layer doping concentration is lower than N2The doping concentration of layer is realized the drop on potential with this, is given
Carrier provides enough kinetic energy and reaches battery the two poles of the earth, improves built in field intensity, short circuit current and transformation efficiency, is conducive to
The separation of carrier.And a more stable gradual change electric field is established on the basis of carrier diffusion and migration, make electric field
Variation more evenly, is conducive to the collection of photo-generated carrier.
Half lamination flexible silicon-based thin film solar battery of the invention and its preparation method, compared with the prior art, advantage and
Beneficial effect is:
1. the preparation method is flexible using novel half lamination that radio frequency magnetron sputtering method prepares a kind of multilayer light trapping structure
Silicon-based film solar cells, deposition process are cleaned and are participated in without toxic gas, it is easy to accomplish to thicknesses of layers and doping concentration
Control.
2. the present invention uses SiC, ZnO, SiO2As multilayer light trapping structure, refractive index is become larger, it is possible to reduce light
Loss, realization make full use of light.
3. half lamination absorber part of the invention uses novel half lamination PININ structure, mentality of designing is in film PIN
I layers of the structure intermediate intrinsic intermediate insertion lower N layers of (N of one layer of doping concentration1Type amorphous silicon layer), sub- battery both may be implemented
Recycling, and can solve the heavy doping problem of tunnel junctions in traditional laminated cell, and realize the graded bandgap of intrinsic layer, change
The shorter problem of the carrier diffusion length that rare book sign a-Si:H is generated, while entire intrinsic region being made to be at built in field again
In.Compared with laminated cell, main advantage is, the multiple utilization of intermediate cell.Compared with unijunction PIN battery, realization pair
The effective use of solar spectrum improves the transfer efficiency and stability of battery.Compared with laminated cell, solves each sub- battery
Current matching problem, the problem of avoiding heavy doping in tunnel junctions, improve the built in field intensity of battery, carrier realized
It is effective to collect and separate, it is thinned cell thickness.Substantially increase the short circuit current and transformation efficiency of battery.Novel half lamination
Open-circuit voltage, short circuit current and the transformation efficiency of battery are all improved.
4. novel silicon base hull cell involved in the present invention, half lamination absorber is former using the potential gradual change in battery
Material uses graded bandgap material in intrinsic layer, combines microcrystal silicon with amorphous silicon material, improve battery to solar spectrum
Utilization rate, deposition method are physical vapour deposition (PVD), and deposition process cleaning is easy to control.
5. half lamination absorber intrinsic part of the invention is that amorphous silicon is combined with microcrystalline silicon materials, to realize graded bandgap
Structure utilizes N1And N2Doping concentration difference realizes the gradual change of potential, to realize battery to solar spectrum short-wave band and long-wave band
Fully absorb.Which improve traditional PIN structural, design philosophy is to design one using potential gradual change principle in battery
The novel half lamination absorber of kind is PI1N1I2N2The flexible silicon-based thin film solar battery of type.
6. a kind of half lamination silicon-base thin-film battery for having multilayer light trapping structure, by introducing three kinds of different materials of refractive index
Expect SiC, ZnO, SiO2And wet etching making herbs into wool is used to it, reduce the reflection and refraction of light.By in original PIN structural
I layer in one layer of doping concentration of insertion it is N layer lower, the carrier diffusion length for improving intrinsic a-Si:H generation shorter is asked
Topic, while it is at entire intrinsic region in built in field, it realizes the multiple utilization of sub- battery, avoids electric in laminated cell
The problem of stream matching and tunnel junctions heavy doping.And intrinsic layer uses graded bandgap, guarantees to sunlight 300-1100nm wavelength model
That encloses fully absorbs, and improves the transfer efficiency and stability of battery.
7. the present invention improves the utilization rate of light by the thickness of improvement intrinsic layer, this is because traditional absorber
When with a thickness of 1um, I1And I2It is amorphous silicon material, it can only be using the visible light within the scope of 300-730nm, by improving I2Layer
Material, by I2It is made into microcrystalline silicon film, entire battery is made to have expanded spectral response, can expand absorbing wavelength is 300-
The sunlight of 1100nm, and the thickness by improving intrinsic layer, improve the utilization rate of light, to improve the conversion effect of battery
Rate.
Detailed description of the invention
Fig. 1 is the basic structure of half lamination flexible silicon-based thin film solar battery in the embodiment of the present invention 1.Wherein, 1- is soft
Property PET substrate, electrode before 2-AZO, 3-Al2O3Buffer layer, half lamination absorber of 4-, 5-SiC buffer layer, 6-ZnO buffer layer, 7-
SiO2Buffer layer, 8-AZO back electrode.
Fig. 2 is the structure of half lamination absorber of half lamination flexible silicon-based thin film solar battery in the embodiment of the present invention 1.
In half lamination absorber part of half lamination flexible silicon-based thin film solar battery, 4.1-P type amorphous silicon layer, the intrinsic amorphous of 4.2-
Silicon layer, 4.3-N1Type amorphous silicon layer, 4.4- intrinsic microcrystalline silicon layer, 4.5-N2Type amorphous silicon layer.
Fig. 3 is that the I-V characteristic of novel half lamination PININ battery and traditional laminate PIN PIN battery of the invention compares song
Line.
Fig. 4 is that the embodiment of the present invention carries out PVD device used by physical vapour deposition (PVD), wherein 11- operates controller,
12- vacuum meter, 13- substrate layer bracket, the assembly of 14- target pedestal, 15- sputter gun, 16- observation window, 17- ultrahigh vacuum+RF/DC electricity
Source.
Fig. 5 is the flow diagram of the preparation process of the novel half lamination flexible silicon-based thin film solar battery of the present invention.
Fig. 6 is the basic structure of half lamination flexible silicon-based thin film solar battery in the embodiment of the present invention 4.Wherein, 9- is not
Become rusty steel plate substrate, electrode before 2-AZO, 3-Al2O3Buffer layer, half lamination absorber of 4-, 5-SiC buffer layer, 6-ZnO buffer layer, 7-
SiO2Buffer layer, 8-AZO back electrode.
Fig. 7 is the structure of half lamination absorber of half lamination flexible silicon-based thin film solar battery in the embodiment of the present invention 4.
In half lamination absorber part of half lamination flexible silicon-based thin film solar battery, 4.1-P type amorphous silicon layer, the intrinsic amorphous of 4.2-
Silicon layer, 4.3-N1Type amorphous silicon layer, 4.4- intrinsic microcrystalline silicon layer, 4.5-N2Type amorphous silicon layer.
Specific embodiment
Below with reference to embodiment, the present invention is described in further detail.
Embodiment 1
A kind of half lamination flexible silicon-based thin film solar battery, structure are that sequentially connected flexible PET plastic is flexible
PET substrate layer 1, using AZO as transparent AZO before electrode 2, be upwards in turn Al2O3Buffer layer 3, half lamination absorber 4, multilayer are fallen into
Photo structure (SiC buffer layer 5, ZnO buffer 6, SiO2Buffer layer 7), AZO back electrode 8, specifically: PET/AZO/Al2O3/P/
I1/N1/I2/N2/SiC/ZnO/SiO2/AZO.The structural schematic diagram of half lamination flexible silicon-based thin film solar battery is shown in Fig. 1, half lap
The structure of layer absorber is shown in Fig. 2.
The absorber is half lamination absorber, is half lamination PI by two sub- battery compositions1N1I2N2Structure,
In, P layers are P-type non-crystalline silicon layer 4.1, I1Layer is intrinsic amorphous silicon layer 4.2, N1Layer is N1Type amorphous silicon layer 4.3, I2Layer is intrinsic
Microcrystal silicon layer 4.4, N2Layer is N2Type amorphous silicon layer 4.5；
N1Doping concentration be 1 × e16cm-3, N2Doping concentration be 2 × e19cm-3。
The multilayer light trapping structure, wherein closer to half lamination absorber, the layer material refractive index of multilayer light trapping structure
It is bigger, refractive index≤half lamination absorber refractive index of the layer material close to half lamination absorber of multilayer light trapping structure,
The number of plies of multilayer material is 3 layers.
The multilayer light trapping structure, layer material are specially SiC layer, ZnO layer and SiO2Layer, SiC layer, ZnO layer and SiO2
Layer is arranged successively by the bigger sequence closer to half lamination absorber of refractive index；
Wherein, the refractive index that the refractive index of SiC is 2.7, ZnO is 2, SiO2Refractive index be 1.5, i.e., with from absorber by
It is proximal and distal, respectively SiC layer, ZnO layer and SiO2Layer.
The film number of plies of the half lamination flexible silicon-based thin film solar battery is 12 layers；
The substrate layer with a thickness of for 0.2mm；
The AZO transparent front electrode with a thickness of 30nm；
The buffer layer with a thickness of 20nm；
The 200nm of the thickness of the back electrode；
The overall thickness of the half lamination absorber be 1.35 μm, wherein P-type non-crystalline silicon layer with a thickness of 10nm, it is intrinsic
Amorphous silicon layer is with a thickness of 300nm, N1Type amorphous silicon layer is with a thickness of 20nm, and intrinsic microcrystalline silicon layer is with a thickness of 1000nm, N2Type amorphous silicon
Layer is with a thickness of 20nm；
The multilayer light trapping structure, SiO2Layer with a thickness of 50nm, ZnO layer with a thickness of 30nm, SiC layer with a thickness of
30nm。
Fig. 5 is shown in a kind of preparation method of half novel lamination flexible silicon-based thin film solar battery, process flow, specifically
Steps are as follows:
The PVD device that the present embodiment uses is shown in Fig. 4, and flexible PET substrate layer is fixed on substrate layer bracket 13, by vacuum meter
12 observations, when vacuum chamber is extracted into high vacuum (< 10-3Pa after), it is passed through argon gas, starts ultrahigh vacuum+RF/DC power supply 17 to generate brightness
Light discharges and generates plasma, the target in target pedestal assembly 14 is bombarded by sputter gun 15, and then deposit different functions
Layer.It is controlled by operating controller 11, is observed by observation window 16.
(1) flexible and transparent PET substrate is provided as substrate layer, by flexible and transparent PET substrate in ultrasonic cleaning instrument
It first uses alcohol washes five minutes, is then cleaned with deionized water, it is stand-by with being dried with nitrogen；
(2) the flexible and transparent PET substrate after cleaning is put into the assembly of the target pedestal in PVD magnetic-controlled sputtering coating equipment 14
On.It in flexible and transparent PET deposition on substrate AZO transparent front electrode and is roughened, technological parameter are as follows: operating pressure
1.0Pa, Ar flow are 30sccm, and sputtering power 100W, operating temperature is 25 DEG C, sedimentation time 30min；
(3) in AZO transparent front electrode depositing Al2O3Buffer layer, technological parameter are as follows: operating pressure 1.0Pa, Ar flow is
30sccm, sputtering power 100W, 40 DEG C of operating temperature, sedimentation time 4-6min；
(4) in Al2O3Buffer layer deposition P-type non-crystalline silicon layer, process conditions are as follows: operating pressure 1.0Pa, Ar and H2Flow point
Not Wei 30sccm and 20sccm, sputtering power 100W, 40 DEG C of operating temperature, sedimentation time 4-6min；
(5) in P-type non-crystalline silicon layer deposition intrinsic amorphous silicon layer, process conditions are as follows: operating pressure 1.0Pa, Ar flow is
30sccm, sputtering power 100W, 25 DEG C of operating temperature, sedimentation time 70-100min；
(6) N is deposited in intrinsic amorphous silicon layer1Type amorphous silicon layer, sedimentary condition are as follows: operating pressure 1.0Pa, Ar and H2Flow
Respectively 30sccm and 20sccm, sputtering power 100W, operating temperature are 25 DEG C, sedimentation time 6-10min；
(7) in N1Type amorphous silicon layer deposition intrinsic micro crystal silicon layer, sedimentary condition are as follows: operating pressure 3Pa, Ar and H2Flow point
Not Wei 20sccm and 40sccm, sputtering power 200W, 120 DEG C of operating temperature, sedimentation time 200-400min；
(8) N is deposited in intrinsic microcrystalline silicon layer2Type amorphous silicon layer, sedimentary condition are as follows: operating pressure 1.0Pa, Ar flow is
30sccm, H2Flow is 20sccm, and sputtering power 100W, operating temperature is 25 DEG C, sedimentation time 6-10min；
(9) in N2Type amorphous silicon layer deposition is sequentially depositing SiC, ZnO, SiO2, wherein SiC with a thickness of 50-80nm, ZnO
With a thickness of 30-50nm, SiO2With a thickness of 30-50nm, and roughening treatment is performed etching to light trapping structure surface.Wherein sink
The operating pressure of product process is 1.0Pa, and Ar flow is 30sccm, and sputtering power 100W, operating temperature is 60 DEG C；Deposition is completed
Roughening treatment is performed etching to surface with dilute hydrochloric acid solution afterwards, time 20min guarantees resulting recess uniform one after etching
It causes and transverse width is 4.0 μm.
(10) AZO back electrode is deposited on multilayer light trapping structure, operating pressure 1.0Pa, Ar flow is 30sccm, sputters function
Rate 100W, operating temperature are 25 DEG C, sedimentation time 30min；
(11) battery is packaged to get the novel half lamination flexible silicon-based thin film solar battery of the present embodiment is arrived,
I-V characteristic test is carried out to prepared battery.Test result is shown in Fig. 3, and special with the I-V of traditional laminate PIN PIN battery
Property compares, from correlation curve, it can be deduced that, novel half lamination flexible silicon-based thin film solar-electricity manufactured in the present embodiment
The short circuit current and open-circuit voltage in pond are increased compared to traditional laminate PIN PIN battery, and short circuit current increases especially
Obviously.
The half lamination flexible silicon-based thin film solar battery open-circuit voltage that the present embodiment is finally prepared up to 1.28V or more,
Short circuit current is up to 19.98mA/cm2More than, fill factor up to 0.84, the stable conversion efficiency of battery is up to 14.25%~
17.36%.
Embodiment 2
A kind of half lamination flexible silicon-based thin film solar battery, structure is that sequentially connected flexibility PI plastics are substrate
Layer, using AZO as transparent front electrode, be upwards in turn ITO buffer layer, half lamination absorber, multilayer light trapping structure (SiC, ZnO,
SiO2), back electrode Ag, specifically: PI/AZO/ITO/P/I1/N1/I2/N2/SiC/ZnO/SiO2/Ag。
The absorber is half lamination absorber, is half lamination PI1N1I2N2Structure, wherein P layers are P-type non-crystalline silicon
Layer, I1Layer is intrinsic amorphous silicon layer, N1Layer is N1Type amorphous silicon layer, I2Layer is intrinsic microcrystalline silicon layer, N2Layer is N2Type amorphous silicon layer；
N1Doping concentration be 2 × e16cm-3, N2Doping concentration be 5 × e19cm-3。
The multilayer light trapping structure, wherein closer to half lamination absorber, the layer material refractive index of multilayer light trapping structure
It is bigger, refractive index≤half lamination absorber refractive index of the layer material close to half lamination absorber of multilayer light trapping structure,
The number of plies of multilayer material is 3 layers.
The multilayer light trapping structure, layer material are specially SiC layer, ZnO layer and SiO2Layer, SiC layer, ZnO layer and SiO2
Layer is arranged successively by the bigger sequence closer to half lamination absorber of refractive index；
Wherein, the refractive index that the refractive index of SiC is 2.7, ZnO is 2, SiO2Refractive index be 1.5, i.e., with from absorber by
It is proximal and distal, respectively SiC layer, ZnO layer and SiO2Layer.
The film number of plies of the half lamination flexible silicon-based thin film solar battery is 12 layers；
The substrate layer with a thickness of for 0.001mm；
The AZO transparent front electrode with a thickness of 50nm；
The buffer layer with a thickness of 10nm；
The 600nm of the thickness of the back electrode；
The overall thickness of the half lamination absorber be 2.55 μm, wherein P-type non-crystalline silicon layer with a thickness of 30nm, it is intrinsic
Amorphous silicon layer is with a thickness of 400nm, N1Type amorphous silicon layer is with a thickness of 30nm, and intrinsic microcrystalline silicon layer is with a thickness of 2000nm, N2Type amorphous silicon
Layer is with a thickness of 45nm；
The multilayer light trapping structure, SiO2Layer with a thickness of 80nm, ZnO layer with a thickness of 50nm, SiC layer with a thickness of
50nm；
A kind of preparation method of half novel lamination flexible silicon-based thin film solar battery, the layer deposited as needed,
Deposition method is the same as embodiment 1.
Embodiment 3
A kind of half lamination flexible silicon-based thin film solar battery, structure are sequentially connected AZO as transparent front electrode,
Half lamination absorber, back electrode AZO, specifically: PET/P/I1/N1/I2/N2/AZO。
The absorber is half lamination absorber, is half lamination PI1N1I2N2Structure, wherein P layers are P-type non-crystalline silicon
Layer, I1Layer is intrinsic amorphous silicon layer, N1Layer is N1Type amorphous silicon layer, I2Layer is intrinsic microcrystalline silicon layer, N2Layer is N2Type amorphous silicon layer；
N1Doping concentration be 1 × e16cm-3, N2Doping concentration be 1 × e19cm-3。
The film number of plies of the half lamination flexible silicon-based thin film solar battery is 7 layers；
The AZO transparent front electrode with a thickness of 30nm；
The 200nm of the thickness of the back electrode；
The overall thickness of the half lamination absorber be 1.85 μm, wherein P-type non-crystalline silicon layer with a thickness of 10nm, it is intrinsic
Amorphous silicon layer is with a thickness of 300nm, N1Type amorphous silicon layer is with a thickness of 20nm, and intrinsic microcrystalline silicon layer is with a thickness of 1500nm, N2Type amorphous silicon
Layer is with a thickness of 20nm；
A kind of preparation method of half novel lamination flexible silicon-based thin film solar battery, the layer deposited as needed,
Deposition method is the same as embodiment 1.
Embodiment 4
A kind of half lamination flexible silicon-based thin film solar battery, structure is that sequentially connected stainless steel plate is stainless steel lining
Bottom 9, AZO back electrode 8 are followed successively by half lamination absorber 4, multilayer light trapping structure (SiC buffer layer 5, ZnO buffer 6, SiO2
Buffer layer 7), Al2O3Buffer layer 3, using AZO as transparent AZO before electrode 2, specifically: stainless steel plate/AZO/N2/I2/N1/I1/
P/SiC/ZnO/SiO2/Al2O3/AZO.The structural schematic diagram of half lamination flexible silicon-based thin film solar battery is shown in Fig. 6, half lamination
The structure of absorber is shown in Fig. 7.
The absorber is half lamination absorber, is half lamination PI1N1I2N2Structure, wherein P layers are P-type non-crystalline silicon
Layer 4.1, I1Layer is intrinsic amorphous silicon layer 4.2, N1Layer is N1Type amorphous silicon layer 4.3, I2Layer is intrinsic microcrystalline silicon layer 4.4, N2Layer be
N2Type amorphous silicon layer 4.5；
N1Doping concentration be 5 × e16cm-3, N2Doping concentration be 5 × e19cm-3。
The multilayer light trapping structure, wherein closer to half lamination absorber, the layer material refractive index of multilayer light trapping structure
It is bigger, refractive index≤half lamination absorber refractive index of the layer material close to half lamination absorber of multilayer light trapping structure,
The number of plies of multilayer material is 3 layers.
The multilayer light trapping structure, layer material are specially SiC layer, ZnO layer and SiO2Layer, SiC layer, ZnO layer and SiO2
Layer is arranged successively by the bigger sequence closer to half lamination absorber of refractive index；
Wherein, the refractive index that the refractive index of SiC is 2.7, ZnO is 2, SiO2Refractive index be 1.5, i.e., with from absorber by
It is proximal and distal, respectively SiC layer, ZnO layer and SiO2Layer.
The film number of plies of the half lamination flexible silicon-based thin film solar battery is 12 layers；
The substrate layer with a thickness of for 0.250mm；
The AZO transparent front electrode with a thickness of 40nm；
The buffer layer with a thickness of 20nm；
The 400nm of the thickness of the back electrode；
The overall thickness of the half lamination absorber be 1.86 μm, wherein P-type non-crystalline silicon layer with a thickness of 10nm, it is intrinsic
Amorphous silicon layer is with a thickness of 300nm, N1Type amorphous silicon layer is with a thickness of 30nm, and intrinsic microcrystalline silicon layer is with a thickness of 1500nm, N2Type amorphous silicon
Layer is with a thickness of 20nm；
The multilayer light trapping structure, SiO2Layer with a thickness of 60nm, ZnO layer with a thickness of 40nm, SiC layer with a thickness of
40nm。
A kind of preparation method of half novel lamination flexible silicon-based thin film solar battery, the layer deposited as needed,
Deposition method is the same as embodiment 1.
Claims (11)
1. a kind of half lamination flexible silicon-based thin film solar battery, structure includes sequentially connected preceding electrode, absorber and back
Electrode；It is characterized in that, the absorber is half lamination absorber, it is half lamination PI1N1I2N2Structure, wherein P layers are P
Type amorphous silicon layer, I1Layer is intrinsic amorphous silicon layer, N1Layer is N-type non-crystalline silicon layer, I2Layer is intrinsic microcrystalline silicon layer, N2Layer is that N-type is non-
Crystal silicon layer；
N1The doping concentration of layer is (1 ~ 5) × 1016cm-3, N2The doping concentration of layer is (1 ~ 5) × 1019cm-3。
2. half lamination flexible silicon-based thin film solar battery according to claim 1, which is characterized in that half lamination
Absorber is the silica-base film material that amorphous silicon and microcrystalline silicon materials combine, is the cascaded structure of plural layers, the tandem junction
Structure be realized after the completion of every layer of film deposition it is concatenated.
3. half lamination flexible silicon-based thin film solar battery according to claim 1, which is characterized in that half lamination
Flexible silicon-based thin film solar battery, structure further include substrate layer, buffer layer and sunken photosphere；When substrate layer is hyaline layer,
The structure of half lamination flexible silicon-based thin film solar battery is sequentially connected transparent substrate, preceding electrode, buffer layer, half lamination
Absorber falls into photosphere and back electrode；And according to light source direction, half lamination absorber is PI1N1I2N2Sequential organization.
4. half lamination flexible silicon-based thin film solar battery according to claim 1, which is characterized in that half lamination
Flexible silicon-based thin film solar battery, structure further include substrate layer, buffer layer and sunken photosphere；When substrate layer is non transparent layer
When, the structure of half lamination flexible silicon-based thin film solar battery is sequentially connected preceding electrode, buffer layer, falls into photosphere, half lamination
Absorber, back electrode and nontransparent substrate layer, and according to light source direction, half lamination absorber is PI1N1I2N2Sequential organization.
5. half lamination flexible silicon-based thin film solar battery according to claim 3 or 4, which is characterized in that described falls into
Photosphere is the multilayer light trapping structure comprising multilayer material, wherein closer to half lamination absorber, the layer material of multilayer light trapping structure
Refractive index is bigger, refractive index≤half lamination absorber folding of the layer material close to half lamination absorber of multilayer light trapping structure
Penetrate rate, the number of plies >=2 layer of multilayer material.
6. half lamination flexible silicon-based thin film solar battery according to claim 5, which is characterized in that the multilayer is fallen into
Every layer material refractive index of photo structure is 1.2-2.7.
7. half lamination flexible silicon-based thin film solar battery according to claim 3 or 4, which is characterized in that the lining
It is flexible and transparent PET or flexible and transparent PI when bottom is hyaline layer；It is stainless steel plate when the substrate layer is non transparent layer；
The preceding electrode is AZO transparent front electrode；
The buffer layer is AZO homogeneous buffer layer or the heterogeneous buffer layer of AZO；When for AZO homogeneous buffer layer, buffer layer is
AZO layers, when buffer layer heterogeneous for AZO, buffer layer Al2O3In buffer layer, Ag buffer layer, Al buffer layer or ITO buffer layer
It is a kind of；
The back electrode is AZO back reflector, golden back electrode, silver-colored one of back electrode or aluminum back electrode.
8. the half lamination flexible silicon-based thin film solar battery according to claim 3 or 4, which is characterized in that described
Overall thickness≤10 μm of half lamination flexible silicon-based thin film solar battery, the film number of plies are 7 ~ 20 layers；
The substrate layer with a thickness of 0.001 ~ 0.250mm；
The preceding electrode with a thickness of 30 ~ 50nm；
The buffer layer with a thickness of 10 ~ 20nm；
200 ~ 600nm of the thickness of the back electrode；
The overall thickness of the half lamination absorber is 1.35 μm -2.55 μm, wherein P-type non-crystalline silicon layer with a thickness of 10 ~
30nm, intrinsic amorphous silicon layer is with a thickness of 300 ~ 400nm, N1Layer N-type non-crystalline silicon layer is with a thickness of 20 ~ 30nm, intrinsic micro crystal silicon thickness
Degree is 1000nm ~ 2000nm, N2Layer N-type non-crystalline silicon layer is with a thickness of 20 ~ 45nm.
9. according to claim 1, half lamination flexible silicon-based thin film solar battery, feature described in any one of 3,4 exist
In the half lamination flexible silicon-based thin film solar battery, short circuit current is up to 18.24 ~ 22.57mA/cm2, half lamination is soft
The stable conversion efficiency of property silicon-based film solar cells is up to 14.25% ~ 17.36%.
10. the preparation method of half lamination flexible silicon-based thin film solar battery described according to claim 1 ~ any one of 8,
Characterized by comprising the following steps:
Step 1: processing substrate layer, the substrate layer that obtains that treated；
Step 2: radio-frequency magnetron sputter method is used on substrate layer, according to the structure of half lamination flexible silicon-based thin film solar battery
It is sequentially depositing each layer, obtains half lamination flexible silicon-based thin film solar battery；Wherein, each layer includes preceding electrode, buffering
Layer, P-type non-crystalline silicon layer, intrinsic amorphous silicon layer, N1 Layer NType amorphous silicon layer, intrinsic microcrystalline silicon layer, N2 Layer NType amorphous silicon layer, multilayer
Light trapping structure and back electrode.
11. the preparation method of half lamination flexible silicon-based thin film solar battery according to claim 10, which is characterized in that
In the step 2, the radio-frequency magnetron sputter method, in Ar and H2It is deposited in mixed-gas environment, wherein Ar and H2Stream
Amount ratio is (30 ~ 40) sccm:(20 ~ 30) sccm.
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| PCT/CN2019/085098 WO2019233223A1 (en) | 2018-06-06 | 2019-04-30 | Semi-laminated flexible silicon-based thin film solar cell and preparation method therefor |
| JP2021514464A JP7109833B2 (en) | 2018-06-06 | 2019-04-30 | SEMI-LAYER FLEXIBLE SILICON-BASED THIN-FILM SOLAR CELL AND MANUFACTURING METHOD THEREOF |
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| US4471155A (en) * | 1983-04-15 | 1984-09-11 | Energy Conversion Devices, Inc. | Narrow band gap photovoltaic devices with enhanced open circuit voltage |
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| JP2002057356A (en) * | 2000-08-10 | 2002-02-22 | Mitsubishi Heavy Ind Ltd | Method for manufacturing silicon solar battery |
| CN201045738Y (en) * | 2006-03-06 | 2008-04-09 | 胡宏勋 | Flexible amorphous silicon thin-film solar cell |
| CN1851935A (en) * | 2006-03-23 | 2006-10-25 | 姜堰新金太阳能光伏制造有限公司 | Double-junction solar cell and manufacturing method thereof |
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