CN108550644A - Half lamination flexible silicon-based thin film solar cell of one kind and preparation method thereof - Google Patents
Half lamination flexible silicon-based thin film solar cell of one kind and preparation method thereof Download PDFInfo
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—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
- 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
- H01L31/048—Encapsulation of modules
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—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
- H01L31/18—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
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- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Abstract
Half lamination flexible silicon-based thin film solar cell 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 cell 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 that processing substrate layer is sequentially depositing each layer according to structure using radio-frequency magnetron sputter method.The half lamination flexible silicon-based thin film solar cell 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, half laminated construction can improve built in field intensity, short circuit current and the transformation efficiency of battery.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 technology
With the increasingly depleted of 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 the a-Si of traditional unijunction PIN amorphous silicon film solar batteries and PINPIN:H/μc-Si:In H stacked solar cell, cascade solar cells
The heavy doping problem of tunnel junctions in the Staebler-Wronski effect and laminate PIN PIN batteries of non-crystalline silicon proposes a kind of half lamination of design
The novel silicon base thin-film solar cell structure of PININ structures.
The best light absorption design of solar battery structure needs to maximize the absorption of intrinsic layer and minimize 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 to face light
Scattering process so that more light is injected into battery, while partly can not will be inhaled as the back electrode of anti-reflection structure
The light reflection of receipts returns 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 non-crystalline 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 ensure to make full use of solar spectrum.
Due to there is the n-p junction opposite with p-n junction, i.e., it is logical inside multijunction cell in traditional laminate PIN PIN batteries
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
Apparent 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 non-crystalline silicon
A large amount of dangling bonds are will produce, 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 make p-n junction become to obtain good conductivity without will produce apparent resistance.And
The realization of heavy doping is always to restrict a bottleneck of laminated cell development in silicon target.
Chinese patent CN201210529409.3 discloses a kind of p-i-n types 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
Layer can improve the mobility of electronics in the n-layer, reduce 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 types that the solar cell, 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 non-crystalline 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 electricity conversion of battery are improved；The disadvantage is that
Battery structure involved by the patent is still traditional PINRPIN laminated cells, can not 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 being combined with i-p bilayer band gap buffer layers by the absorbed layer of band gap consecutive variations, with effective
The recombination probability of carrier is reduced, while surface treatment is carried out to back reflector and forms micro-nano structure, to be effectively increased 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 elements in film are realized using chemical vapor deposition method, and doping concentration is not easy to control.
Invention content
The present invention is for the problems of above-mentioned, it is proposed that a kind of half lamination flexible silicon-based thin film solar cell and its
Preparation method, the half lamination flexible silicon-based thin film solar cell 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 present invention can improve the built in field of battery by half laminated construction on the basis of thinned laminated cell thickness
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.
The present invention half lamination flexible silicon-based thin film solar cell of one kind, 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 non-crystalline 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 cell, structure further include substrate layer, buffer layer and sunken photosphere；
Wherein, whether transparent according to substrate layer, it is 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 cell 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 in order 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 electrodes；
Preferably, the buffer layer is AZO homogeneous buffer layers or the heterogeneous buffer layers of AZO；When for AZO homogeneous buffer layers
When, buffer layer is AZO layers, when buffer layer heterogeneous for AZO, buffer layer Al2O3Buffer layer, Ag buffer layers, Al buffer layers or
One kind in ITO buffer layers；
Preferably, the back electrode is in AZO back reflectors, 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 cell is：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, specially：
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 cell, the film number of plies are 7~20 layers；
The thickness of the substrate layer is 0.001~0.250mm；
The thickness of the preceding electrode is 30~50nm；
The thickness of the buffer layer is 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 the thickness of P-type non-crystalline silicon layer is 10
~30nm, intrinsic amorphous silicon layer thickness are 300~400nm, N1Type amorphous silicon layer thickness is 20~30nm, intrinsic micro crystal silicon thickness
Degree is 1000nm~2000nm, N2Type amorphous silicon layer thickness is 20~45nm；
The multilayer light trapping structure, SiO2The thickness of layer is 50~80nm, and the thickness of ZnO layer is 30~50nm, SiC layer
Thickness be 30~50nm.
The half lamination flexible silicon-based thin film solar cell, short circuit current is up to 18.24~22.57mA/cm2, half
The stable conversion efficiency of lamination flexible silicon-based thin film solar cell is up to 14.25%~17.36%.
A kind of preparation method of half lamination flexible silicon-based thin film solar cell of the present invention, includes the following steps：
Step 1：Substrate layer is handled, 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 cell
Structure is sequentially depositing each layer, obtains half lamination flexible silicon-based thin film solar cell；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, a kind of half lamination flexible silicon-based thin film solar cell of the invention
Preparation method includes the following steps：
Step 1：Transparent substrate is handled, the transparent substrate that obtains that treated；
Step 2：Electrode before being sequentially depositing using radio-frequency magnetron sputter method on transparent substrate, 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 cell.
In the step 2, the sunken photosphere uses wet etching making herbs into wool, ensures 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 cell
Method includes the following steps：
Step 1：Substrate layer is handled, the substrate layer that obtains that treated；
Step 2：Electrode before being sequentially depositing using radio-frequency magnetron sputter method on substrate layer, 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 cell.
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 cell of one kind of the invention
Preparation method, include the following steps：
Step 1：Nontransparent substrate layer is handled, the nontransparent substrate layer that obtains that treated；
Step 2：Back electrode, N are 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 cell.
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 layers of sub- battery 1 and the P layers 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 is reduced towards the direction of knot, and carrier is primarily generated at intrinsic
The areas floor I, the N of novel half laminated cell1Layer doping concentration is less 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 evenly, is conducive to the collection of photo-generated carrier.
The present invention half lamination flexible silicon-based thin film solar cell and its preparation method, compared with the prior art, advantage and
Advantageous effect is：
1. the preparation method prepares a kind of novel half lamination flexibility of multilayer light trapping structure using radio frequency magnetron sputtering method
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 becomes 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 structures, mentality of designing is in film PIN
I layers of structure intermediate intrinsic is intermediate to be inserted into the 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 problems, such as the heavy doping of tunnel junctions in traditional laminated cell, and realize the graded bandgap of intrinsic layer, change
Rare book levies a-Si:The shorter problem of carrier diffusion length that 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 batteries, realization pair
Solar spectrum efficiently uses, and 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 detach, 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. involved novel silicon base hull cell in the present invention, half lamination absorber uses the potential gradual change in battery former
Material uses graded bandgap material in intrinsic layer, so that microcrystal silicon is combined 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.
It is combined with microcrystalline silicon materials 5. the half lamination absorber intrinsic part of the present invention is non-crystalline silicon, 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 cell of type.
6. a kind of half lamination silicon-base thin-film battery having multilayer light trapping structure, the three kind materials different by introducing 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 layers in be inserted into one layer of doping concentration it is N layers lower, improve intrinsic a-Si:The carrier diffusion length of H generations is shorter to ask
Topic, while entire intrinsic region being made to be in built in field again, 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, ensures to sunlight 300-1100nm wavelength models
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 thickness is 1um, I1And I2It is amorphous silicon material, the visible light within the scope of 300-730nm can only be utilized, by improving I2Layer
Material, by I2Microcrystalline silicon film is made, entire battery is made to have expanded spectral response, it is 300- that can expand absorbing wavelength
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.
Description of the drawings
Fig. 1 is the basic structure of half lamination flexible silicon-based thin film solar cell in the embodiment of the present invention 1.Wherein, 1- is soft
Property PET substrate, electrode before 2-AZO, 3-Al2O3Buffer layer, half lamination absorbers of 4-, 5-SiC buffer layers, 6-ZnO buffer layers, 7-
SiO2Buffer layer, 8-AZO back electrodes.
Fig. 2 is the structure of half lamination absorber of half lamination flexible silicon-based thin film solar cell in the embodiment of the present invention 1.
In half lamination absorber part of half lamination flexible silicon-based thin film solar cell, 4.1-P type amorphous silicon layers, the intrinsic amorphous of 4.2-
Silicon layer, 4.3-N1Type amorphous silicon layer, 4.4- intrinsic microcrystalline silicon layers, 4.5-N2Type amorphous silicon layer.
Fig. 3 is that the I-V characteristic comparison of the novel half lamination PININ batteries and traditional laminate PIN PIN batteries of the present invention is bent
Line.
Fig. 4 is that the embodiment of the present invention carries out PVD devices used by physical vapour deposition (PVD), wherein 11- operation and control devices,
12- vacuum meters, 13- substrate layer brackets, the assembly of 14- target pedestals, 15- sputter guns, 16- observation windows, 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 cell of the present invention.
Fig. 6 is the basic structure of half lamination flexible silicon-based thin film solar cell 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 absorbers of 4-, 5-SiC buffer layers, 6-ZnO buffer layers, 7-
SiO2Buffer layer, 8-AZO back electrodes.
Fig. 7 is the structure of half lamination absorber of half lamination flexible silicon-based thin film solar cell in the embodiment of the present invention 4.
In half lamination absorber part of half lamination flexible silicon-based thin film solar cell, 4.1-P type amorphous silicon layers, the intrinsic amorphous of 4.2-
Silicon layer, 4.3-N1Type amorphous silicon layer, 4.4- intrinsic microcrystalline silicon layers, 4.5-N2Type amorphous silicon layer.
Specific implementation mode
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 cell, 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 layers 5, ZnO buffer 6, SiO2Buffer layer 7), AZO back electrodes 8, specially：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 cell 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, multilayer light trapping structure close to half lamination absorber layer material refractive index≤half lamination absorber refractive index,
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 in order 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 cell is 12 layers；
The thickness of the substrate layer is 0.2mm；
The thickness of the AZO transparent front electrodes is 30nm；
The thickness of the buffer layer is 20nm；
The 200nm of the thickness of the back electrode；
The overall thickness of the half lamination absorber is 1.35 μm, wherein the thickness of P-type non-crystalline silicon layer is 10nm, intrinsic
Amorphous silicon layer thickness is 300nm, N1Type amorphous silicon layer thickness is 20nm, and intrinsic micro crystal silicon layer thickness is 1000nm, N2Type non-crystalline silicon
Layer thickness is 20nm；
The multilayer light trapping structure, SiO2The thickness of layer is 50nm, and the thickness of ZnO layer is 30nm, and the thickness of SiC layer is
30nm。
Fig. 5 is shown in a kind of preparation method of half novel lamination flexible silicon-based thin film solar cell, technological process, specifically
Steps are as follows：
The PVD devices that the present embodiment uses are shown in Fig. 4, and flexible PET substrate layer is fixed on substrate layer bracket 13, by vacuum meter
12 observation, when vacuum chamber be extracted into high vacuum (<10-3Pa after), it is passed through argon gas, starts ultrahigh vacuum+RF/DC power supplys 17 to generate brightness
Light discharges and generates plasma, bombards the target in target pedestal assembly 14 by sputter gun 15, and then deposit different functions
Layer.It is controlled by operation and control device 11, is observed by observation window 16.
(1) flexible and transparent PET substrates are provided as substrate layer, by flexible and transparent PET substrates in ultrasonic cleaning instrument
It first uses alcohol washes five minutes, is then cleaned with deionized water, dried up with nitrogen for use；
(2) the flexible and transparent PET substrates after cleaning are put into the assembly of the target pedestal in PVD magnetic-controlled sputtering coating equipments 14
On.It in flexible and transparent PET deposition on substrate AZO transparent front electrodes and is roughened, technological parameter is：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 Als2O3Buffer layer, technological parameter are：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：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：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：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：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：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 the thickness of SiC is 50-80nm, ZnO
Thickness be 30-50nm, SiO2Thickness be 30-50nm, and roughening treatment is performed etching to light trapping structure surface.It is wherein heavy
The operating pressure of product process is 1.0Pa, and Ar flows are 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 ensures the recess uniform one of gained after etching
It causes and transverse width is 4.0 μm.
(10) AZO back electrodes are deposited on multilayer light trapping structure, operating pressure 1.0Pa, Ar flow is 30sccm, sputters work(
Rate 100W, operating temperature are 25 DEG C, sedimentation time 30min；
(11) battery is packaged to get to the novel half lamination flexible silicon-based thin film solar cell of the present embodiment,
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 batteries
Property is compared, 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 batteries, and short circuit current increases especially
Obviously.
The half lamination flexible silicon-based thin film solar cell 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 cell, structure is that sequentially connected flexibility PI plastics are substrate
Layer, using AZO as transparent front electrode, be upwards in turn ITO buffer layers, half lamination absorber, multilayer light trapping structure (SiC, ZnO,
SiO2), back electrode Ag, specially：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, multilayer light trapping structure close to half lamination absorber layer material refractive index≤half lamination absorber refractive index,
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 in order 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 cell is 12 layers；
The thickness of the substrate layer is 0.001mm；
The thickness of the AZO transparent front electrodes is 50nm；
The thickness of the buffer layer is 10nm；
The 600nm of the thickness of the back electrode；
The overall thickness of the half lamination absorber is 2.55 μm, wherein the thickness of P-type non-crystalline silicon layer is 30nm, intrinsic
Amorphous silicon layer thickness is 400nm, N1Type amorphous silicon layer thickness is 30nm, and intrinsic micro crystal silicon layer thickness is 2000nm, N2Type non-crystalline silicon
Layer thickness is 45nm；
The multilayer light trapping structure, SiO2The thickness of layer is 80nm, and the thickness of ZnO layer is 50nm, and the thickness of SiC layer is
50nm；
A kind of preparation method of half novel lamination flexible silicon-based thin film solar cell, 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 cell, structure are sequentially connected AZO as transparent front electrode,
Half lamination absorber, back electrode AZO, specially：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 cell is 7 layers；
The thickness of the AZO transparent front electrodes is 30nm；
The 200nm of the thickness of the back electrode；
The overall thickness of the half lamination absorber is 1.85 μm, wherein the thickness of P-type non-crystalline silicon layer is 10nm, intrinsic
Amorphous silicon layer thickness is 300nm, N1Type amorphous silicon layer thickness is 20nm, and intrinsic micro crystal silicon layer thickness is 1500nm, N2Type non-crystalline silicon
Layer thickness is 20nm；
A kind of preparation method of half novel lamination flexible silicon-based thin film solar cell, 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 cell, structure is that sequentially connected stainless steel plate is stainless steel lining
Bottom 9, AZO back electrodes 8 are followed successively by half lamination absorber 4, multilayer light trapping structure (SiC buffer layers 5, ZnO buffer 6, SiO2
Buffer layer 7), Al2O3Buffer layer 3, using AZO as transparent AZO before electrode 2, specially：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 cell 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, multilayer light trapping structure close to half lamination absorber layer material refractive index≤half lamination absorber refractive index,
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 in order 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 cell is 12 layers；
The thickness of the substrate layer is 0.250mm；
The thickness of the AZO transparent front electrodes is 40nm；
The thickness of the buffer layer is 20nm；
The 400nm of the thickness of the back electrode；
The overall thickness of the half lamination absorber is 1.86 μm, wherein the thickness of P-type non-crystalline silicon layer is 10nm, intrinsic
Amorphous silicon layer thickness is 300nm, N1Type amorphous silicon layer thickness is 30nm, and intrinsic micro crystal silicon layer thickness is 1500nm, N2Type non-crystalline silicon
Layer thickness is 20nm；
The multilayer light trapping structure, SiO2The thickness of layer is 60nm, and the thickness of ZnO layer is 40nm, and the thickness of SiC layer is
40nm。
A kind of preparation method of half novel lamination flexible silicon-based thin film solar cell, the layer deposited as needed,
Deposition method is the same as embodiment 1.
Claims (10)
1. a kind of half lamination flexible silicon-based thin film solar cell, structure includes sequentially connected preceding electrode, absorber and the back of the body
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 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。
2. half lamination flexible silicon-based thin film solar cell as described in claim 1, which is characterized in that half lamination is inhaled
Acceptor is the silica-base film material that non-crystalline silicon and microcrystalline silicon materials combine, is the cascaded structure of plural layers, the cascaded structure
Be realized after the completion of every layer of film deposition it is concatenated.
3. half lamination flexible silicon-based thin film solar cell as described in claim 1, which is characterized in that half lamination is soft
Property silicon-based film solar cells, structure further includes substrate layer, buffer layer and sunken photosphere；Wherein, whether saturating according to substrate layer
It is bright, it is divided into two kinds of connection types：When substrate layer is hyaline layer, the structure of half lamination flexible silicon-based thin film solar cell be according to
The transparent substrate of secondary connection, buffer layer, half lamination absorber, falls into photosphere and back electrode at preceding electrode；When substrate layer is nontransparent
When layer, the structure of half lamination flexible silicon-based thin film solar cell is sequentially connected preceding electrode, buffer layer, falls into photosphere, half lap
Layer absorber, back electrode and nontransparent substrate layer, and according to light source direction, half lamination absorber is PI1N1I2N2Sequence is tied
Structure.
4. half lamination flexible silicon-based thin film solar cell as claimed in claim 3, which is characterized in that the sunken photosphere is
Include the multilayer light trapping structure of multilayer material, wherein closer to half lamination absorber, the layer material refractive index of multilayer light trapping structure
It is bigger, multilayer light trapping structure close to half lamination absorber layer material refractive index≤half lamination absorber refractive index,
The number of plies >=2 layer of multilayer material.
5. half lamination flexible silicon-based thin film solar cell as claimed in claim 4, which is characterized in that the multilayer falls into light
Every layer material refractive index of structure is 1.2-2.7.
6. half lamination flexible silicon-based thin film solar cell as claimed in claim 3, which is characterized in that the substrate layer is
It is flexible and transparent PET or flexible and transparent PI when hyaline layer；It is stainless steel plate when the substrate layer is non transparent layer；
The preceding electrode is AZO transparent front electrodes；
The buffer layer is AZO homogeneous buffer layers or the heterogeneous buffer layers of AZO；When for AZO homogeneous buffer layers, buffer layer is
AZO layers, when buffer layer heterogeneous for AZO, buffer layer Al2O3In buffer layer, Ag buffer layers, Al buffer layers or ITO buffer layers
It is a kind of；
The back electrode is one kind in AZO back reflectors, golden back electrode, silver-colored back electrode or aluminum back electrode.
7. half lamination flexible silicon-based thin film solar cell as described in claim 3, which is characterized in that half lamination
Overall thickness≤10 μm of flexible silicon-based thin film solar cell, the film number of plies are 7~20 layers；
The thickness of the substrate layer is 0.001~0.250mm；
The thickness of the preceding electrode is 30~50nm；
The thickness of the buffer layer is 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 the thickness of P-type non-crystalline silicon layer be 10~
30nm, intrinsic amorphous silicon layer thickness are 300~400nm, N1Type amorphous silicon layer thickness is 20~30nm, intrinsic micro crystal silicon layer thickness
For 1000nm~2000nm, N2Type amorphous silicon layer thickness is 20~45nm.
8. the half lamination flexible silicon-based thin film solar cell as described in any one of claim 1 or 3, which is characterized in that
The half lamination flexible silicon-based thin film solar cell, short circuit current is up to 18.24~22.57mA/cm2, half lamination flexibility
The stable conversion efficiency of silicon-based film solar cells is up to 14.25%~17.36%.
9. the preparation method of the half lamination flexible silicon-based thin film solar cell as described in any one of claim 1~7,
It is characterized in that, includes the following steps：
Step 1：Substrate layer is handled, 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 cell
It is sequentially depositing each layer, obtains half lamination flexible silicon-based thin film solar cell；Wherein, each layer includes preceding electrode, buffering
Layer, P-type non-crystalline silicon layer, intrinsic amorphous silicon layer, N1Type amorphous silicon layer, intrinsic microcrystalline silicon layer, N2Type amorphous silicon layer, multilayer fall into light knot
Structure and back electrode.
10. the preparation method of half lamination flexible silicon-based thin film solar cell as claimed in claim 9, which is characterized in that institute
In the step 2 stated, the radio-frequency magnetron sputter method, in Ar and H2It is deposited in mixed-gas environment, wherein Ar and H2Flow
Ratio is (30~40) sccm：(20~30) sccm.
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| 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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| CN113540289A (en) * | 2021-07-13 | 2021-10-22 | 广东工业大学 | Preparation method of solar cell film for broadening photoresponse waveband |
| CN113540289B (en) * | 2021-07-13 | 2023-01-13 | 广东工业大学 | Preparation method of solar cell film for broadening photoresponse waveband |
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| WO2019233223A1 (en) | 2019-12-12 |
| CN108550644B (en) | 2019-10-25 |
| JP7109833B2 (en) | 2022-08-01 |
| JP2021523580A (en) | 2021-09-02 |
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