CN105990466A - Manufacturing method of Schottky type vertical nanowire array solar cell - Google Patents
Manufacturing method of Schottky type vertical nanowire array solar cell Download PDFInfo
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- CN105990466A CN105990466A CN201510055914.2A CN201510055914A CN105990466A CN 105990466 A CN105990466 A CN 105990466A CN 201510055914 A CN201510055914 A CN 201510055914A CN 105990466 A CN105990466 A CN 105990466A
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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
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
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Abstract
The invention discloses a manufacturing method of a Schottky type vertical nanowire array solar cell. The method includes the following steps that: based on a metal catalyst, a vertical semiconductor nanowire array is grown on a heavily-doped single-crystal substrate through using a molecular epitaxial method, wherein the single-crystal substrate is a back electrode; and a transparent conductive layer contacting with the metal catalyst is produced on the vertical semiconductor nanowire array, wherein the transparent conductive layer is a top electrode, and the vertical semiconductor nanowire array is a light absorption layer and an antireflection layer. According to the manufacturing method of the invention, a high-conversion efficiency solar cell can be manufactured through a using simple process with low cost.
Description
Technical field
The present invention relates to technical field of solar batteries, particularly relate to the system of Schottky type vertical nano-wire array solar cells
Make method.
Background technology
Currently, day by day exhausted due to fossil energies such as coal, oil, natural gass, and a large amount of poisonous and harmful of burning and exhausting and
Greenhouse gases, the regenerative resource of cleaning is all being endeavoured to find in countries in the world.And solar energy due to pollution-free and with not to the utmost
Feature, the solar battery technology directly converted to available electric energy receives the extensive concern of common people.
Early sun energy battery technology is with silica-based panel solar battery as representative, although business-like unijunction silicon solar cell
Transformation efficiency reached about 18%, but its cost of electricity-generating is the highest；Second filial generation solaode is conceived to reduce material
Cost, as used the relatively low CIGS thin-film material of price, although expense decreases, but electricity conversion is but
Drop to about 10%.A new generation's solar battery technology reduces cost while then will be devoted to keep high conversion.
Photo-generated carrier is mainly separated and collection by solaode by the potential barrier of the material of different fermi levels.Its gesture
The formation built mainly has pn-junction mode, but pn-junction needs complicated processing technology, is therefore unfavorable for the reduction of cost.
Summary of the invention
The embodiment of the present invention provides the manufacture method of a kind of Schottky type vertical nano-wire array solar cells, in order to realize profit
With simple process low-cost production height transformation efficiency solaode, the method includes:
Use metallic catalyst by the method growth of vertical semiconductor nanowires of molecule extension in heavily doped single crystal substrates
Array；
Described vertical semiconductor nano-wire array makes the transparency conducting layer contacting described metallic catalyst；
Wherein, described single crystal substrates is back electrode, and described transparency conducting layer is top electrode, described vertical semiconductor nanometer linear array
It is classified as light absorbing zone and antireflection layer.
In one embodiment, described vertical semiconductor nano-wire array makes the electrically conducting transparent contacting described metallic catalyst
Layer, including:
Spin coating organic media in described vertical semiconductor nano-wire array, uses the method for etching to expose described metal catalytic
Agent；
The metallic catalyst of each nano wire is connected at transparency conducting layer described in deposited atop.
In one embodiment, spin coating organic media in described vertical semiconductor nano-wire array, including: described vertical half
Spin coating SU8 glue or PMMA (polymethyl methacrylate) glue in nanowires array；
And/or, use the method for etching to expose described metallic catalyst, including: use oxygen, argon or carbon tetrafluoride etc.
The method of plasma etching exposes described metallic catalyst.
In one embodiment, described metallic catalyst includes: aluminum, gold, platinum, palladium or nickel.
In one embodiment, described single crystal substrates includes: at the bottom of silicon, GaAs, cadmium selenide or indium phosphide.
In one embodiment, described vertical semiconductor nano-wire array includes: silicon, GaAs, indium phosphide or cadmium selenide nano
Linear array.
In one embodiment, described transparency conducting layer includes: tin indium oxide, aluminium-doped zinc oxide or Fluorin doped ZnO transparent
Conductive layer.
In the embodiment of the present invention, utilize Schottky contacts gesture natural between metallic catalyst and vertical semiconductor nano-wire array
Build, with the single crystal substrates of vertical semiconductor nanowire array growth as back electrode, with vertical semiconductor nano-wire array work itself
For light absorbing zone and antireflection layer, it is only necessary to simple top electrode making step can make solaode, with pn-junction side
Formula is compared, although the theoretical electricity conversion of the two is close, but Schottky contacts simplifies technique, converts keeping height
Cost is reduced while rate；Meanwhile, in order to absorb incident illumination to greatest extent, solar cell surface need to make antireflection layer,
The antireflection layer three dimensional structure being made up of vertical semiconductor nano-wire array has splendid anti-reflection characteristic, thus is more suitable for carrying
The electricity conversion of high solar battery.
Accompanying drawing explanation
In order to be illustrated more clearly that the embodiment of the present invention or technical scheme of the prior art, below will be to embodiment or existing skill
In art description, the required accompanying drawing used is briefly described, it should be apparent that, the accompanying drawing in describing below is only the present invention
Some embodiments, for those of ordinary skill in the art, on the premise of not paying creative work, it is also possible to root
Other accompanying drawing is obtained according to these accompanying drawings.In the accompanying drawings:
Fig. 1 is the schematic diagram of the manufacture method of Schottky type vertical nano-wire array solar cells in the embodiment of the present invention；
Fig. 2 is the exemplary plot of the GaAs nanowire solar cells making gold catalysis in the embodiment of the present invention；
Fig. 3 is the i-v curve figure of Si nano-wire array Schootky scolar cell in the embodiment of the present invention；
Fig. 4 is the i-v curve figure of GaAs nano-wire array Schootky scolar cell in the embodiment of the present invention；
Fig. 5 is the i-v curve figure of InP nano-wire array Schootky scolar cell in the embodiment of the present invention；
Fig. 6 is the i-v curve figure of CdSe nano-wire array Schootky scolar cell in the embodiment of the present invention.
Detailed description of the invention
For making the purpose of the embodiment of the present invention, technical scheme and advantage clearer, real to the present invention below in conjunction with the accompanying drawings
Execute example to be described in further details.Here, the schematic description and description of the present invention is used for explaining the present invention, but not
As limitation of the invention.
Inventor is it is considered that compared with pn-junction mode, use metal to make solar energy with the Schottky contacts mode of quasiconductor
Battery, although the theoretical electricity conversion of the two is close, but pn-junction needs complicated processing technology, is therefore unfavorable for
The reduction of cost；On the contrary, Schottky contacts then simplifies technique, can reduce cost while keeping high conversion.With
Time, in order to absorb incident illumination to greatest extent, solar cell surface often needs to make the antireflection layer of three dimensional structure.And manage
Opinion all proves with practice, and the three dimensional structure being made up of the array such as nano wire, nanometer rods has a splendid anti-reflection characteristic, thus more
It is applicable to improve the electricity conversion of solaode.Based on this, in order to realize converting with simple process low-cost production height
The purpose of efficiency solaode, provides a kind of Schottky type vertical nano-wire array solar cells in the embodiment of the present invention
Manufacture method, as it is shown in figure 1, the method may include that
Step 101, the method growth of vertical using metallic catalyst to pass through molecule extension in heavily doped single crystal substrates are partly led
Body nano-wire array；
Step 102, on described vertical semiconductor nano-wire array make contact described metallic catalyst transparency conducting layer；
Wherein, described single crystal substrates is back electrode, and described transparency conducting layer is top electrode, and described vertical semiconductor nano-wire array is
Light absorbing zone and antireflection layer.
When being embodied as, described vertical semiconductor nano-wire array makes the electrically conducting transparent contacting described metallic catalyst
Layer, may include that spin coating organic media in described vertical semiconductor nano-wire array, uses the method for etching to expose institute
State metallic catalyst；The metallic catalyst of each nano wire is connected at transparency conducting layer described in deposited atop.
In embodiment, in described vertical semiconductor nano-wire array during spin coating organic media, can use applicable according to demand
Organic media, such as can in described vertical semiconductor nano-wire array organic Jie such as spin coating SU8 glue or PMMA glue
Matter.When the method using etching exposes described metallic catalyst, it is also possible to select the specifically side of etching being suitable for according to demand
Method, such as, can use the method for the plasma etchings such as oxygen, argon or carbon tetrafluoride to expose described metallic catalyst.
Visible, the manufacture method of the Schottky type vertical nano-wire array solar cells of the embodiment of the present invention, make use of metal
Schottky contact barrier natural between catalyst and vertical semiconductor nano-wire array, utilizes vertical semiconductor nano-wire array
The substrate of growth is back electrode, utilizes vertical semiconductor nano-wire array itself as light absorbing zone and anti-reflection layer simultaneously, it is only necessary to
Want simple top electrode making step can make solaode, thus i.e. ensure that high electricity conversion, in turn simplify
Technique, reduces cost.
Below as a example by the GaAs nanowire solar cells making gold catalysis, the technology road of embodiment of the present invention method is described
Line.Fig. 2 shows technical scheme in this example, including: (1), gold nano grain are deposited in monocrystal silicon substrate；(2)、
Molecule epitaxial growth vertical GaAs nano-wire array；(3), deposition interlayer insulating layer (organic media)；(4), at gold
Deposition transparent conductive electrode near catalyst granules.
With reference to shown in Fig. 2, embodiment may include that and use the method for molecule extension heavily doped with different metal for catalyst
Growth of vertical conductor nano tube/linear array in miscellaneous single crystal substrates；Spin coating organic media in nano-wire array, and use etching
Method by metallic catalyst expose；Finally deposit the transparency conducting layer of only contacting metal catalyst.This solaode is with weight
The single crystal substrates of doping is back electrode, with contact transparency conducting layer on metallic catalyst as top electrode, with nano-wire array
Itself utilizes the Schottky contacts high efficiency separation photoproduction between metallic catalyst and nano wire to carry as light absorbing zone and anti-reflection layer
Stream.Complete back electrode merely with one step of nanowire growth during enforcement, schottky junctions touches antireflection layer three system
Make process, it is only necessary to increase simple top electrode processing technology, it is thus achieved that convert effect with simple process low-cost production height
The purpose of rate solaode.
When being embodied as, metallic catalyst can use the metals such as aluminum, gold, platinum, palladium or nickel.Single crystal substrates can use silicon,
The substrates such as GaAs, cadmium selenide or indium phosphide.Vertical semiconductor nano-wire array can use silicon, GaAs, indium phosphide or
The nano-wire arrays such as cadmium selenide.Transparency conducting layer can use tin indium oxide, aluminium-doped zinc oxide or Fluorin doped zinc oxide etc. saturating
Bright conductive layer.
Name the making side of the Schottky type vertical nano-wire array solar cells of the instantiation explanation embodiment of the present invention
Method.
Embodiment one: with aluminum as catalyst, uses chemical vapour deposition technique to grow about in highly doped n-type (111) silicon base
10 microns of long silicon nanowire arrays.Spin coating SU8 glue on silicon nanowire array, about 15 microns of thickness, and by oxygen etc. from
SU8 glue is thinned to ＜ 10 microns by daughter, exposes Al catalysts granule.Magnetron sputtering technique is used to deposit 1 on surface
The indium tin oxide transparent conductive layer that micron is thick, obtains the efficient vertical solaode of silicon nanowire array Schottky type, its typical case
Photoelectric respone curve can be as shown in Figure 3.Fig. 3 is the i-v curve of Si nano-wire array Schootky scolar cell.
Open-circuit voltage 0.57V, short circuit current 36.1mAcm-2, fill factor, curve factor 34%, efficiency about 7.0%.
Embodiment two: with gold as catalyst, uses chemical vapour deposition technique to grow about in heavily-doped p-type (111) silicon base
5 microns long GaAs nano-wire arrays.Spin coating SU8 glue on GaAs nano-wire array, about 8 microns of thickness, and pass through argon
SU8 glue is thinned to ＜ 5 microns by gas plasma, exposes Au catalyst granule.Use magnetron sputtering technique heavy on surface
Long-pending 1 micron of thick aluminium-doped zinc oxide transparent conductive layer, obtains the efficient GaAs vertical solar energy of nano-wire array Schottky type
Battery, its typical photoelectric respone curve can be as shown in Figure 4.Fig. 4 is GaAs nano-wire array Schottky solar-electricity
The i-v curve in pond.Open-circuit voltage 0.7V, short circuit current 52.5mAcm-2, fill factor, curve factor 30%, efficiency about 11%.
Embodiment three: with platinum as catalyst, uses chemical vapour deposition technique raw in highly doped n-type (111) GaAs substrate
It is about 20 microns long indium phosphide nano linear arrays.Spin coating SU8 glue in indium phosphide nano linear array, about 25 microns of thickness, and
By oxygen gas plasma, SU8 glue is thinned to ＜ 20 microns, exposes Pt catalyst granule.Use magnetron sputtering technique
Deposit 1 micron of thick Fluorin doped ZnO transparent conductive layer on surface, obtain efficient indium phosphide nano linear array Schottky type and hang down
Straight solaode, its typical photoelectric respone curve can be as shown in Figure 5.Fig. 5 be InP nano-wire array Schottky too
The i-v curve of sun energy battery.Open-circuit voltage 0.37V, short circuit current 34mAcm-2, fill factor, curve factor 31.5%, efficiency
About 3.96%.
Embodiment four: with palladium as catalyst, uses chemical vapour deposition technique raw in heavily-doped p-type (111) cadmium selenide substrate
It is about 2 microns long cadmium selenide nano linear arrays.Spin coating PMMA glue in cadmium selenide nano linear array, about 5 microns of thickness,
And by carbon tetrafluoride plasma, PMMA glue is thinned to ＜ 2 microns, expose palladium catalyst granule.Use magnetic control spatters
Technology of penetrating deposits 1 micron of thick indium tin oxide transparent conductive layer on surface, obtains efficient cadmium selenide nano linear array Schottky type
Vertical solaode, its typical photoelectric respone curve can be as shown in Figure 6.Fig. 6 is CdSe nano-wire array Xiao Te
The i-v curve of based solar battery.Open-circuit voltage 0.28V, short circuit current 34.2mAcm-2, fill factor, curve factor 46%,
Efficiency about 4.4%.
In sum, the embodiment of the present invention in order to reach with the purpose of easy technique low-cost production high performance solar batteries, with
Different metal is that catalyst uses the method for molecule extension to grow semiconductor nanowires in heavily doped single crystal substrates, and is receiving
The transparency conductive electrode of contacting metal catalyst is made on nanowire arrays；With heavily doped substrate as back electrode, with contact at gold
Transparency conducting layer on metal catalyst is top electrode, utilizes the Schottky contacts between metallic catalyst and nano wire to obtain the sun
Can battery.The embodiment of the present invention is the most applicable to various semiconductor nanowires, and technique is simple, it is not necessary to complicated pn-junction system
Make technology.And nano wire itself has good extinction effect, it is not necessary to the anti-reflection layer in later stage makes, thus has low one-tenth
Originally, high efficiency advantage.
Concrete, the embodiment of the present invention completes back electrode, Schottky contact barrier and antireflective while growth nano wire
Three manufacturing process of layer, only need a simple top electrode of step to make the manufacturing process i.e. completing solaode, thus simplify
Technique, contributes to reducing cost.Between metallic catalyst and the nano wire of induction nanowire growth, there is contacting of atom level,
Greatly reduce the effect that surface fermi level freezes, there is preferable Schottky contact barrier, thus help in raising photoelectricity
Transformation efficiency.
The targeted customer of the solaode manufacturing technology of the embodiment of the present invention can include the building under " green housing " theory
Roof and exterior wall generating, illumination in the ecological agriculture, irrigate generating etc., be increasingly subject to environmental problem puzzlement China and
His developing country has the most wide application prospect.
Particular embodiments described above, has been carried out the most specifically the purpose of the present invention, technical scheme and beneficial effect
Bright, be it should be understood that the specific embodiment that the foregoing is only the present invention, the protection being not intended to limit the present invention
Scope, all within the spirit and principles in the present invention, any modification, equivalent substitution and improvement etc. done, should be included in
Within protection scope of the present invention.
Claims (7)
1. the manufacture method of a Schottky type vertical nano-wire array solar cells, it is characterised in that including:
Use metallic catalyst by the method growth of vertical semiconductor nanowires of molecule extension in heavily doped single crystal substrates
Array；
Described vertical semiconductor nano-wire array makes the transparency conducting layer contacting described metallic catalyst；
Wherein, described single crystal substrates is back electrode, and described transparency conducting layer is top electrode, described vertical semiconductor nanometer linear array
It is classified as light absorbing zone and antireflection layer.
2. the method for claim 1, it is characterised in that make on described vertical semiconductor nano-wire array and connect
Touch the transparency conducting layer of described metallic catalyst, including:
Spin coating organic media in described vertical semiconductor nano-wire array, uses the method for etching to expose described metal catalytic
Agent；
The metallic catalyst of each nano wire is connected at transparency conducting layer described in deposited atop.
3. method as claimed in claim 2, it is characterised in that spin coating has in described vertical semiconductor nano-wire array
Machine medium, including: spin coating SU8 glue or polymetylmethacrylate in described vertical semiconductor nano-wire array
Glue；
And/or, use the method for etching to expose described metallic catalyst, including: use oxygen, argon or carbon tetrafluoride etc.
The method of plasma etching exposes described metallic catalyst.
4. the method as described in any one of claims 1 to 3, it is characterised in that described metallic catalyst includes: aluminum,
Gold, platinum, palladium or nickel.
5. the method as described in any one of claims 1 to 3, it is characterised in that described single crystal substrates includes: silicon, arsenic
Change at the bottom of gallium, cadmium selenide or indium phosphide.
6. the method as described in any one of claims 1 to 3, it is characterised in that described vertical semiconductor nano-wire array
Including: silicon, GaAs, indium phosphide or cadmium selenide nano linear array.
7. the method as described in any one of claims 1 to 3, it is characterised in that described transparency conducting layer includes: oxidation
Indium stannum, aluminium-doped zinc oxide or Fluorin doped ZnO transparent conductive layer.
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| CN110112060A (en) * | 2019-05-20 | 2019-08-09 | 山东大学 | A method of III-V race's semiconductor nanowires direction of growth of high-performance is controlled using gas-solid-solid growth pattern |
| CN110890444A (en) * | 2019-11-14 | 2020-03-17 | 深圳第三代半导体研究院 | GaN ultraviolet detector and preparation method thereof |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110112060A (en) * | 2019-05-20 | 2019-08-09 | 山东大学 | A method of III-V race's semiconductor nanowires direction of growth of high-performance is controlled using gas-solid-solid growth pattern |
| CN110890444A (en) * | 2019-11-14 | 2020-03-17 | 深圳第三代半导体研究院 | GaN ultraviolet detector and preparation method thereof |
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Application publication date: 20161005 |