CN110224033A - A kind of the iron oxide light anode system and preparation method of embedded silicon pn-junction - Google Patents
A kind of the iron oxide light anode system and preparation method of embedded silicon pn-junction Download PDFInfo
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- CN110224033A CN110224033A CN201910521496.XA CN201910521496A CN110224033A CN 110224033 A CN110224033 A CN 110224033A CN 201910521496 A CN201910521496 A CN 201910521496A CN 110224033 A CN110224033 A CN 110224033A
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- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 title claims abstract description 158
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 title claims abstract description 112
- 239000010703 silicon Substances 0.000 title claims abstract description 112
- 229910052710 silicon Inorganic materials 0.000 title claims abstract description 108
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- 239000000758 substrate Substances 0.000 claims abstract description 34
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 10
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 8
- 229910052796 boron Inorganic materials 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 7
- 238000007254 oxidation reaction Methods 0.000 claims description 7
- 238000000231 atomic layer deposition Methods 0.000 claims description 5
- 239000002131 composite material Substances 0.000 claims description 5
- 229910052742 iron Inorganic materials 0.000 claims description 5
- 229910052758 niobium Inorganic materials 0.000 claims description 5
- 239000010955 niobium Substances 0.000 claims description 5
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims description 5
- 229910052751 metal Inorganic materials 0.000 claims description 4
- 230000003647 oxidation Effects 0.000 claims description 4
- 239000007787 solid Substances 0.000 claims description 4
- 238000009826 distribution Methods 0.000 claims description 3
- 238000005516 engineering process Methods 0.000 claims description 3
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims description 3
- 229910001887 tin oxide Inorganic materials 0.000 claims description 3
- 238000005260 corrosion Methods 0.000 claims description 2
- 230000007797 corrosion Effects 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 230000005641 tunneling Effects 0.000 claims description 2
- 238000003764 ultrasonic spray pyrolysis Methods 0.000 claims description 2
- 238000009413 insulation Methods 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 20
- 230000001699 photocatalysis Effects 0.000 abstract description 14
- 238000006243 chemical reaction Methods 0.000 abstract description 3
- 239000000463 material Substances 0.000 description 8
- 230000000694 effects Effects 0.000 description 6
- 238000005286 illumination Methods 0.000 description 5
- 238000010521 absorption reaction Methods 0.000 description 4
- 210000004027 cell Anatomy 0.000 description 4
- 229910052814 silicon oxide Inorganic materials 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 238000009792 diffusion process Methods 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 230000031700 light absorption Effects 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 230000005693 optoelectronics Effects 0.000 description 3
- 230000006798 recombination Effects 0.000 description 3
- 238000005215 recombination Methods 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- VBMVTYDPPZVILR-UHFFFAOYSA-N iron(2+);oxygen(2-) Chemical group [O-2].[Fe+2] VBMVTYDPPZVILR-UHFFFAOYSA-N 0.000 description 2
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000000149 penetrating effect Effects 0.000 description 2
- 230000005622 photoelectricity Effects 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 238000006722 reduction reaction Methods 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- NNJVILVZKWQKPM-UHFFFAOYSA-N Lidocaine Chemical compound CCN(CC)CC(=O)NC1=C(C)C=CC=C1C NNJVILVZKWQKPM-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 229910021607 Silver chloride Inorganic materials 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 230000001143 conditioned effect Effects 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000284 extract Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 229960004194 lidocaine Drugs 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 229910000484 niobium oxide Inorganic materials 0.000 description 1
- URLJKFSTXLNXLG-UHFFFAOYSA-N niobium(5+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Nb+5].[Nb+5] URLJKFSTXLNXLG-UHFFFAOYSA-N 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- 238000007540 photo-reduction reaction Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 210000004508 polar body Anatomy 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 238000004626 scanning electron microscopy Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 229910003145 α-Fe2O3 Inorganic materials 0.000 description 1
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- H01L31/02—Details
- H01L31/0224—Electrodes
- H01L31/022408—Electrodes for devices characterised by at least one potential jump barrier or surface barrier
- H01L31/022425—Electrodes for devices characterised by at least one potential jump barrier or surface barrier for solar cells
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Abstract
The invention belongs to photoelectric conversions and new energy field, to solve the technical issues of iron oxide light anode can not achieve complete photocatalytic water in the prior art, it is proposed the iron oxide light anode system and preparation method of a kind of embedded silicon pn-junction, including iron oxide absorbed layer, p-type silicon doped layer, n-type silicon substrate, back conductive layer, back waterproof insulating layer；The p-type silicon doped layer and n-type silicon substrate constitutes silicon pn-junction；The pattern of silicon pn-junction is pyramid array structure；Electrically conducting transparent tunnel layer is provided between p-type silicon doped layer and iron oxide absorbed layer.Embedded silicon pn-junction makes silicon layer generate biggish photovoltage when absorbing incident light, this photovoltage will form series relationship with iron oxide absorbed layer, the voltage for being equivalent to this size additional is in iron oxide layer, the cut-in voltage of iron oxide light anode will be effectively reduced, the conductivity of iron oxide absorbed layer and its collection efficiency of photo-generated carrier are improved, to realize complete photocatalytic water.
Description
Technical field
The present invention relates to a kind of iron oxide light anode system of embedded silicon pn-junction and preparation methods more particularly to the light anode
Energy band interface control technique when for complete photocatalytic water belongs to photoelectric conversion and new energy field.
Background technique
It is that one kind is expected to be achieved at low cost photocatalytic water by solar energy with the photoelectrochemical cell of photoelectricity extremely core
The effective way of hydrogen manufacturing.The photo-generated carrier that it is generated by semiconductor material absorption sunlight participates in the oxidation and reduction of water
Reaction (generates hydrogen), that is, completes the green fuel that solar energy is converted to high-energy.
Currently, photoelectrochemical cell hydrogen manufacturing but receives many technical difficulties in application.Wherein, critical issue is
The optoelectronic pole material of the overwhelming majority can not rely solely on solar energy and realize photocatalytic water (needing additional certain bias).Although
A small number of semiconductor material with wide forbidden band (such as KTaO3) be theoretically able to achieve complete photocatalytic water (not needing applying bias), but this
A little materials can only absorb ultraviolet light, that is to say, that most sunlights is cannot to be utilized.In addition, these broad stopbands are partly led
The stability of body material in aqueous solution is poor.In order to obtain compared with the photoelectrochemical cell system of high solar transfer efficiency, photoelectricity
Pole material will have moderate forbidden bandwidth, and have good chemical stability in aqueous solution.
Iron oxide (α-Fe2O3) have been shown to have excellent chemical stability, suitable forbidden bandwidth (1.9~2.3eV,
Theoretic transfer efficiency can be to 12.9%~16.8%), the features such as good environment compatibility, be ideal light anode material
Material.However, its minority carrier life time is shorter, cause the photo-generated carrier generated (more than several hundred nanometers) when iron oxide is thicker cannot be by
It effectively extracts and collects.In addition, its conduction band potential position is lower than H+/H2Potential causes light induced electron not to be able to satisfy under no-bias
Photo-reduction water react (both iron oxide light anode system can not achieve complete photocatalytic water).To solve the above-mentioned problems, commonly
Method is that other one layer of light absorbing layer is introduced below iron oxide absorbed layer, by the energy band position for combining inside and outside light absorption layer material
Set the thermodynamic requirement for theoretically meeting complete photocatalytic water.The photoelectrochemical cell system constructed by double absorption layer, although
It can theoretically realize complete photocatalytic water, but since interior absorbed layer and photovoltage caused by outer absorbed layer hetero-junctions are less than normal, and
Seriously cause the photoelectric current of entire optoelectronic pole system smaller due to absorbing the Carrier recombination on bed boundary in inside/outside, leads to reality
Test photoelectric current very little when being difficult really to realize complete photocatalytic water or no-bias.
Summary of the invention
The present invention is to solve iron oxide light anode in the prior art to can not achieve complete photocatalytic water, and iron oxide and other light are inhaled
It receives the unmatched problem of double absorption layer optoelectronic pole energy band that layer is constructed and leads to the skill that Carrier recombination is serious, photovoltage is less than normal
Art problem.The technical solution adopted is as follows:
A kind of iron oxide light anode system of embedded silicon pn-junction, the light anode are composite bed type structure, and feature exists
In: along light incident direction successively include iron oxide absorbed layer, p-type silicon doped layer, n-type silicon substrate, back conductive layer, back waterproof it is exhausted
Edge layer；The p-type silicon doped layer and n-type silicon substrate constitutes silicon pn-junction；The pattern of silicon pn-junction is pyramid array structure；P-type
It is provided with electrically conducting transparent tunnel layer between silicon doped layer and iron oxide absorbed layer, electrically conducting transparent tunnel layer thickness phase everywhere
Deng.
Preferably iron oxide layer with a thickness of 50~150nm；
Boron doped concentration range is 5.0 × (10 preferably in p-type silicon doped layer18~1019)cm-3, depth be 0.1~
0.3μm。
The concentration range of p-doped is 5.0 × (10 preferably in n-type silicon substrate14~1015)cm-3, substrate thickness be 200~
600μm。
Preferably electrically conducting transparent tunneling layer thickness is 10~50nm.
Preferably pyramid array be solid matter pattern, size in a certain range random distribution (i.e. height for 0.5~3 μm,
Bottom edge length is 0.7~4 μm).
Silicon pn-junction is embedded in above scheme, and that silicon layer can be made to generate biggish photovoltage when absorbing incident light is (and individual
N or p-type silicon doped layer are to can not achieve this function), this photovoltage will form series relationship with iron oxide absorbed layer, be equivalent to
The cut-in voltage of iron oxide light anode will be effectively reduced in iron oxide layer in the voltage of this additional size.Silicon pn-junction is pyramid
Pattern, the geometrical characteristic of pyramid formation looks described herein are any pyramids such as pyramid, including triangular pyramid, rectangular pyramid；Golden word
Tower formation looks can (1) make it is subsequent by the iron oxide layer grown on it be micro-nano structure, so that iron oxide be greatly improved
The specific surface area of film and the efficiency of light absorption in its unit volume of enhancing；(2) though penetrating the intensity of the sunlight of iron oxide layer
So there is obvious decaying, but the light absorpting ability of silicon layer can be enhanced in the processing of pyramid patternization, so that photoproduction carries in silicon
Flow the quantity of son and the photo-generated carrier in oxide layer quite (if the corresponding photo-generated carrier quantity of the two differs greatly, quantity
A significantly less side will determine the output performance of entire light anode).What is be arranged between p-type silicon doped layer and iron oxide layer is transparent
Bring energy band mismatch problem and silicon/iron oxide circle when conductive tunnel layer can directly contact to avoid p-type silicon and iron oxide
The serious problem of Carrier recombination at face.In addition, the metallic element in electrically conducting transparent tunnel layer is alternatively arranged as mixing for iron oxide layer
The conductivity of iron oxide layer and its collection efficiency of photo-generated carrier can be improved in miscellaneous source, so that the effect of complete photocatalytic water can be realized
Fruit.
A kind of preparation side of the iron oxide light anode system of embedded silicon pn-junction is also provided based on the above technical solution
Method, comprising the following steps:
A. using N-shaped (100) silicon wafer as substrate, silicon pyramid array is prepared using alkaline wet corrosion silicon technology；
B. boron doping is carried out on silicon pyramid array, obtains p-type silicon doped layer；
C. using silicon pn-junction pyramid as substrate, using atomic layer deposition (ALD) technology growth electrically conducting transparent tunnel layer；
D. iron oxide absorbed layer is grown with ultrasonic spray pyrolysis in electrically conducting transparent tunnelling layer surface；
E. conductive layer is made at the back side of n-type silicon substrate, and draws external conducting wire；
F. waterproof insulating layer is coated on the electrically conductive.
Further, in step c, metallic element in electrically conducting transparent tunnel layer when carrying out step d can thermal expansion be dissipated to oxygen
Change in iron absorbed layer.So that the electric property of the iron oxide absorbed layer grown is more preferably.Preferably electrically conducting transparent tunnel layer is to mix
The tin oxide of niobium, since niobium or other opposite metallic elements of tin are easier to diffuse in iron oxide absorbed layer, and can be to iron oxide
Form n-type doping.
Further, in step a, the preferred concentration range of n-type silicon p-doped is 5.0 × (1014~1015)cm-3.Silicon gold word
Tower array is close arrangement, size random distribution (being highly 0.5~3 μm, bottom edge length is 0.7~4 μm) in a certain range.
On the one hand this feature can guarantee that silicon pn-junction pyramid array has good limit luminous effect, big specific surface area, while can be with
Guarantee that the electrically conducting transparent tunnel layer of subsequent growth and iron oxide absorbed layer are conformally coated on silicon pn-junction pyramid (and bottom completely
It is not all right when edge lengths are too small and height is too high).
Further, in step b, boron doped preferred concentration range is 5.0 × (1018~1019)cm-3, junction depth 0.1
~0.3 μm.The doping concentration and junction depth of this range can form the excellent pn-junction of electric property with n-type silicon, can produce biggish light
Voltage.
Further, in step c, transparency conducting layer with a thickness of 10~50nm.Transparency conducting layer can be effectively isolated at this time
Silicon and iron oxide form tunnel layer, promote the collection of photohole and light induced electron in silicon pn-junction in iron oxide.
Further, in step d, iron oxide absorbed layer with a thickness of 50~150nm.The light absorption of iron oxide is too when too thin
Weak, photo-generated carrier too far from surface in iron oxide cannot be extracted since its diffusion length is limited when too thick.
Using the above scheme the advantages of, has:
(1) with the silicon pn-junction of pyramid pattern for interior absorbed layer, it ensure that the outer absorbed layer of the iron oxide of subsequent growth also has
There is pyramidal pattern, so that entire light anode has good sunken luminous effect and big specific surface area.
(2) silicon layer is built into pn-junction, when silicon can be made to absorb the incident light for penetrating iron oxide layer, generates biggish light
Voltage.This photovoltage and iron oxide absorbed layer form series relationship, can effectively facilitate the separation of photo-generated carrier in iron oxide layer
And its water oxidation reaction on surface.
(3) electrically conducting transparent is grown with wearing layer between silicon and iron oxide using ALD technique, it is ensured that the transparent of growth is led
Electricity is conformally deposited on silicon pyramid surface with layer is worn, and thickness can control to 0.1nm, and then ensures electrically conducting transparent with wearing layer
Uniformity, interface passivation effect and carrier are with wearing effect.
The above description is only an overview of the technical scheme of the present invention, in order to better understand the technical means of the present invention,
And can be implemented in accordance with the contents of the specification, with presently preferred embodiments of the present invention and attached drawing is cooperated to be described in detail below.
Detailed description of the invention
Fig. 1: the structural schematic diagram of the iron oxide light anode of embedded silicon pn-junction；
Wherein: 1-1 is n-type silicon substrate, and 1-2 is p-type silicon doped layer；1-3 is electrically conducting transparent tunnel layer, and 1-4 is iron oxide
Absorbed layer, 1-5 are back conductive layer, and 1-6 is waterproof insulating layer；
Fig. 2: the scanning electron microscope diagram of the silicon pn-junction of pyramid pattern；
Fig. 3: the scanning electron microscopy after successively grown electrically conducting transparent tunnel layer and iron oxide absorbed layer in silicon pn-junction
Mirror figure；
Fig. 4: iron oxide layer is grown in light sun constructed when the silicon pn-junction substrate of FTO substrate and pyramid array respectively
The I-E characteristic of polar body system；Wherein: 4-1 is grown in the silicon pn-junction substrate when institute structure of pyramid array for iron oxide layer
The dark-state I-E characteristic for the light anode system built；4-2 is the silicon pn-junction substrate that iron oxide layer is grown in pyramid array
When I-E characteristic under AM1.5G illumination of constructed light anode system；4-3 is that iron oxide layer is grown in FTO substrate
When constructed light anode system dark-state I-E characteristic；4-4 is grown in constructed when FTO substrate for iron oxide layer
I-E characteristic of the light anode system under AM1.5G illumination.Current -voltage curve is several in the case of paying attention to two kinds of 4-1 and 4-3
It is overlapped.
Specific embodiment
In order to illustrate more clearly of invention, it is further described with reference to the accompanying drawings and embodiments:
Embodiment one
A kind of iron oxide light anode system of embedded silicon pn-junction, the light anode is composite bed type structure as shown in Figure 1:,
It successively include iron oxide absorbed layer 1-4, p-type silicon doped layer 1-2, n-type silicon substrate 1-1, back conductive layer 1- along light incident direction
5, waterproof insulating layer 1-6 is carried on the back；The p-type silicon doped layer and n-type silicon substrate constitutes silicon pn-junction: (1) pattern of silicon pn-junction is gold
Word tower array structure；(2) electrically conducting transparent tunnel layer 1-3, institute are provided between p-type silicon doped layer 1-2 and iron oxide absorbed layer 1-4
Thickness is equal everywhere for the electrically conducting transparent tunnel layer stated.
The iron oxide light anode system of embedded silicon pn-junction proposed by the invention can completely photocatalytic water working principle it is as follows:
When the sunlight of wide spectrum is incident to photoanode surface, due to the sunken luminous effect of surface pyramid structure, most incident lights
Into inside light anode, shortwave and long wave are oxidized iron layer and silicon layer absorption respectively, and the incident light of 1100nm or more is then by light sun
The back conductive layer of pole reflects back, and leaves from light anode upper surface.The incident light that silicon layer absorbs generates photo-generated carrier, in pn-junction
It is efficiently separated under the promotion of built in field, while can observe a biggish photovoltage (electric field side under open-circuit condition
Top layer is directed toward to by light anode bottom).Photo-generated carrier in iron oxide layer then obtains in the depletion layer near solid/liquid interfaces
It efficiently separates.Photohole in iron oxide layer is extracted to the oxidation reaction that solid/liquid interfaces participate in water；It is generated in silicon pn-junction
Light induced electron then passes through back electrode and is transported to the reduction reaction for participating in water to electrode；In light induced electron and silicon pn-junction in iron oxide
Photohole then pass through electrically conducting transparent tunnel layer and bury in oblivion.The oxidation reaction and reduction reaction of water reach equilibrium state when institute
Corresponding carrier line shows as observed density of photocurrent.
Embodiment two
A kind of preparation method of the iron oxide light anode system of embedded silicon pn-junction, comprising the following steps:
1) it uses resistivity for the n-type silicon chip of 1~5 Ω cm, carries out standard RCA clean.
2) it in the mixed solution of potassium hydroxide and isopropanol, is reacted 60 minutes at 80 DEG C, N-shaped is obtained after cleaning silicon chip
Silicon pyramid array structure, as shown in Figure 2.
3) thermal diffusion mode is used, boron doping, doping concentration 2.0 are carried out to n-type silicon pyramid array obtained by step 2)
×1019cm-3, junction depth 200nm.The n silicon back side is protected when thermal diffusion, so that boron doping is only in silicon pyramid structure
Front occurs.
4) preparation-obtained silicon pn-junction pyramid array is put into the intracavitary of atomic layer deposition system, with four (diformazan ammonia
Base) tin is tin source, tertiarybutylimido base three (lignocaine) niobium is niobium source, alternating growth difference cycle-index is (as being respectively 50
With 5, be repeated 10 times) tin oxide and niobium oxide.
5) gained sample is carried out to 600 DEG C to handle 30 minutes in air atmosphere, surface is obtained and is covered by transparency conducting layer
Silicon pn-junction.
6) above-mentioned sample is put into ullrasonic spraying coating system, using 0.005mol/L ferric nitrate as precursor liquid, at 80 DEG C
Substrate on, to be carried out atomizing spraying 30 minutes under the injection rate of 0.5mL/min.
7) sample that above-mentioned steps obtain is put into tubular annealing furnace, is heat-treated 2 hours at 700 DEG C, atmosphere is
Air.The oxidation iron composite structure of embedded silicon pn-junction is obtained, as shown in Figure 3.
8) in obtained composite construction backside coating In-Ga conductive layer, and external conducting wire is drawn.
9) 704 silica gel are coated, conductive layer is covered completely, obtains final light anode.
10) light anode prepared is immersed in the NaOH aqueous solution of 1mol/L, is to electrode, Ag/ with gauze platinum electrode
AgCl electrode is reference electrode, connects this three electrode using electrochemical workstation, is built into three electrode test systems.
I-E characteristic is tested under darkroom or AM1.5G (standard solar simulator) irradiation respectively.In addition, introducing
Conditioned growth (is not introduced into silicon pn-junction and electrically conducting transparent tunnelling in FTO substrate with identical technique for control experiment, i.e. iron oxide layer
Layer), then it is processed into complete light anode system.As shown in figure 4,4-1 is that iron oxide layer is grown in pyramid array
Silicon pn-junction substrate when constructed light anode system dark-state I-E characteristic；4-2 is that iron oxide layer is grown in pyramid
I-E characteristic of the constructed light anode system under AM1.5G illumination when the silicon pn-junction substrate of array；4-3 is oxidation
Iron layer is grown in the dark-state I-E characteristic of light anode system constructed when FTO substrate；4-4 is grown in for iron oxide layer
I-E characteristic of the constructed light anode system under AM1.5G illumination when FTO substrate.As can be seen that two class samples are equal
There is apparent photoresponse.Under dark-state, the electric current of two samples is almost overlapped with voltage curve, electric in given voltage range
Stream is almost 0.Under AM1.5G illumination, contrast sample is greater than 0.15V in bias (i.e. light anode and to the potential difference between electrode)
When just there is obvious photoelectric current.And the target sample that the present invention program is proposed then has already appeared when bias is -0.3V significantly
Density of photocurrent, and as the increase photoelectric current of bias obviously increases.When zero-bias, the photoelectric current of target sample reaches 0.4mA/
cm2, and the photoelectric current of contrast sample is negligible.These data illustrate to use the iron oxide light anode system of the present invention program can be with
Realize significant complete photocatalytic water, and the iron oxide light anode system being grown directly upon in FTO substrate then cannot.
Claims (6)
1. a kind of iron oxide light anode system of embedded silicon pn-junction, the light anode is composite bed type structure, it is characterised in that:
It successively include iron oxide absorbed layer, p-type silicon doped layer, n-type silicon substrate, back conductive layer, back waterproof insulation along light incident direction
Layer；The p-type silicon doped layer and n-type silicon substrate constitutes silicon pn-junction；The pattern of silicon pn-junction is pyramid array structure；P-type silicon
It is provided with electrically conducting transparent tunnel layer between doped layer and iron oxide absorbed layer, electrically conducting transparent tunnel layer thickness phase everywhere
Deng.
2. the iron oxide light anode system of embedded silicon pn-junction according to claim 1, it is characterised in that: the pyramid battle array
It is classified as solid matter pattern, random distribution.
3. the iron oxide light anode system of embedded silicon pn-junction according to claim 2, it is characterised in that: electrically conducting transparent tunnelling
Layer is the tin oxide for mixing niobium.
4. the iron oxide light anode system of embedded silicon pn-junction described according to claim 1~one of 3, it is characterised in that: oxidation
Iron layer with a thickness of 50~150nm；Boron doped concentration range is 5.0 × (10 in p-type silicon doped layer18~1019)cm-3, depth
It is 0.1~0.3 μm, the concentration range of p-doped is 5.0 × (10 in n-type silicon substrate14~1015)cm-3, substrate thickness be 200~
600 μm, electrically conducting transparent tunneling layer thickness is 10~50nm.
5. a kind of preparation method of the iron oxide light anode system of embedded silicon pn-junction, it is characterised in that: the following steps are included:
A. silicon pyramid array is prepared in n-type silicon substrate using alkaline wet corrosion silicon technology；
B. boron doping is carried out on silicon pyramid array, obtains p-type silicon doped layer；P-type silicon doped layer and n-type silicon substrate constitute silicon
Pn-junction；
C. using silicon pyramid array as substrate, electrically conducting transparent tunnel layer is grown using technique for atomic layer deposition；
D. iron oxide absorbed layer is grown with ultrasonic spray pyrolysis in electrically conducting transparent tunnelling layer surface；
E. conductive layer is made at the back side of n-type silicon substrate, and draws external conducting wire；
F. waterproof insulating layer is coated on the electrically conductive.
6. the preparation method of the iron oxide light anode system of embedded silicon pn-junction according to claim 5, it is characterised in that:
In step c, metallic element in electrically conducting transparent tunnel layer when carrying out step d can thermal expansion be dissipated in iron oxide absorbed layer；
In step a, the concentration range of n-type silicon substrate p-doped is 5.0 × (1014~1015)cm-3；
In step b, boron doped concentration range is 5.0 × (1018~1019)cm-3, junction depth is 0.1~0.3 μm；
In step c, electrically conducting transparent tunnel layer with a thickness of 10~50nm；
In step d, iron oxide absorbed layer with a thickness of 50~150nm.
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