CN109881250A - A kind of monocrystalline silicon inverted pyramid array structure flannelette and its preparation method and application - Google Patents
A kind of monocrystalline silicon inverted pyramid array structure flannelette and its preparation method and application Download PDFInfo
- Publication number
- CN109881250A CN109881250A CN201910086667.0A CN201910086667A CN109881250A CN 109881250 A CN109881250 A CN 109881250A CN 201910086667 A CN201910086667 A CN 201910086667A CN 109881250 A CN109881250 A CN 109881250A
- Authority
- CN
- China
- Prior art keywords
- polymer microballoon
- substrate
- preparation
- mask layer
- film
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- 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
The present invention provides monocrystalline silicon surface inverted pyramid array structure flannelettes and its preparation method and application.Specifically, the present invention provides a kind of preparation methods of monocrystalline silicon surface inverted pyramid array structure flannelette, comprising: generates polymer microballoon single thin film at least one main surface of the substrate, obtains substrate-polymer microballoon single thin film；Mask layer is generated on the substrate-polymer microballoon single thin film, obtains substrate-polymer microballoon single thin film-mask layer；The polymer microballoon in the substrate-polymer microballoon single thin film-mask layer is removed, the main surface is made to expose multiple units of non-mask film covering；The unit that corrosion does not cover the exposure mask is reverse pyramid indent, and inverted pyramid array structure flannelette is obtained in the main surface of the substrate.The present invention prepares the disadvantages of inverted pyramid array structure flannelette method and process is simple, and low in cost, overcoming the prior art can not generate on a large scale, and preparation condition requires harshness.
Description
This case is point filed on May 9th, 2014, application No. is CN201410196601.4 Chinese invention patent application
Case application.
Technical field
The present invention relates to micro-nano manufacture field, in particular to a kind of monocrystalline silicon inverted pyramid array structure flannelette and its preparation
Methods and applications.
Background technique
With the fast development of global economy, demand of the mankind to the energy increasingly increases, and active development new energy is at working as
One of the major subjects in the modern whole world.Solar energy is by leaps and bounds to go on as a kind of very important renewable and clean energy resource
World arena, along with the emergence of photovoltaic industry, solar cell bring green electric power supply just gradually changes people's lives
Mode.Future is in order to increase solar cell power generation ratio in the entire power system, it is necessary to further decrease it and be produced into
This, and improve battery efficiency.Ultra-thin crystal silicon solar battery (10 μm) can greatly reduce the cost of raw material, and keep higher light
Photoelectric transformation efficiency represents one of the developing direction of the following efficient solar battery.Based on the limitation of the battery physical thickness, tradition
The etching method (pyramid structure of 3-10 μm of depth) of crystal silicon is obviously unable to satisfy the needs of ultra-thin crystal silicon solar battery.Nanometer
The silicon substrates such as line, nano-pillar micro-nano structure becomes the hot spot of efficiently sunken optical arena research because it is with excellent sunken light characteristic.However
Above-mentioned micro-nano suede structure can increase along with very big specific surface area, especially reach specific anti-reflection effect structure its
Surface area is usually 10 times of plate silicon area or more, considerably increases the recombination probability of photo-generated carrier on the surface of the material, leads
Cause the reduction of battery efficiency.
Currently, the research group of Massachusetts Institute Technology has found a kind of new method, efficient photoelectricity treater can kept to turn
While changing efficiency, the thickness of silicon wafer is reduced 90% or more, main method is exactly to use interference lithography (interference
Lithography) and wet etching technique forms the light trapping structure of " inverted pyramid ", and each inverted pyramid in thin silicon wafer
The basal diameter of shape indent is no more than 1 micron, and depth is only 300nm.This inverted pyramid structure makes the table of ultra-thin silicon crystal silicon
Area only increases by 70%, and photonic absorption ability but traditional silicon crystal comparable to 30 times thick can make the thickness of c-Si battery in 5-
30 μm, theoretical calculation and test data show that the photoelectric properties parameter of the battery can be with the battery performance phase of 300 μm of traditional technologies
Analogy.However above-mentioned processing process based on two-beam interference is complicated, expensive, can not still adapt to industrialize big rule
Mould production, therefore find that a kind of cheap, fast and efficiently nanometer inverted pyramid etching technics is even more important.
Still lack at present it is satisfactory, cheap rapidly and efficiently, the nanometer that can adapt to industrialization large-scale production falls
Pyramid flannelette etching technics, therefore, there is an urgent need in the art to develop it is cheap rapidly and efficiently, to can adapt to industrialization extensive
The etching technics of the inverted pyramid array structure flannelette of production.
Summary of the invention
The present invention provides it is a kind of cheap rapidly and efficiently, the system of the monocrystalline silicon suede that adapts to industrialization large-scale production
Preparation Method.
In the first aspect of the present invention, a kind of preparation method of monocrystalline silicon suede is provided, the method includes walking as follows
It is rapid:
(a) polymer microballoon single thin film is generated at least one main surface of substrate, obtains substrate-polymer microballoon
Single thin film；
(b) mask layer is generated on the substrate-polymer microballoon single thin film, obtains substrate-polymer microballoon single layer
Film-mask layer；
(c) polymer microballoon in the substrate-polymer microballoon single thin film-mask layer is removed, the main surface is made
Expose multiple units of non-mask film covering；
(d) corrosion does not cover the unit of the exposure mask, reverse pyramid indent is formed it into, thus in the institute of the substrate
It states and obtains inverted pyramid array structure flannelette in main surface.
In another preferred example, the generating mode of the mask layer includes: sputtering, plasma activated chemical vapour deposition, electricity
Beamlet evaporation, hot evaporation, atom sediment, or combinations thereof.
In another preferred example, the mask layer with a thickness of 10~80nm, preferably, the mask layer with a thickness of 20
~60nm.
It in another preferred example, is 0 using the generation temperature that plasma chemical vapor deposition technology generates the mask layer
~120 DEG C, preferably, being 80~100 DEG C.
In another preferred example, the big of the inverted pyramid indent can be controlled by regulation corrosive liquid concentration and etching time
It is small.
In another preferred example, the step (a) includes:
The polymer microballoon film of the orderly period arrangement of single layer is generated by self-assembling technique；
The polymer microballoon film is taped against at least one main surface of the substrate.
In another preferred example, the self-assembling technique includes: surface tension self assembly, electrostatic self-assembled, drift method, electricity
Field induction self assembly.
In another preferred example, the polymer microballoon is polymer nanocomposite ball, and the diameter of the polymer nanocomposite ball is
50~1000nm.
In another preferred example, the polymer nanocomposite ball includes: that polystyrene nanospheres, poly-methyl methacrylate vinegar are received
Rice ball, or combinations thereof.
In another preferred example, the diameter of the polymer nanocomposite ball is 200~700nm.
In another preferred example, the step (a) includes:
A surface is provided with hydrophilic substrate；
The polymer microballoon film of the orderly period arrangement of single layer is generated by drift method；
There is hydrophilic substrate to be put into the liquid level floating solution for having polymer microballoon film the surface, fishes for described poly-
Main surface of the conjunction object microballoon film to the substrate.
In another preferred example, the surface has the preparation of hydrophilic substrate the following steps are included: carrying out to substrate
It is activated, makes the substrate surface that there is hydrophily.
In another preferred example, the dodecyl that it is 10~20% in volume ratio by the substrate that the activation processing, which refers to,
1~4h is impregnated in sulfonic acid sodium water solution.
In another preferred example, the liquid of the floating solution for having polymer microballoon film of the liquid level is reduced by liquid level sedimentation
Face, so that the polymer microballoon film to be deposited to the substrate surface placed in advance.
In another preferred example, the step (c) the following steps are included:
Polymer microballoon described in pyrolytic makes the main surface expose multiple units of non-mask film covering；And/or
Ultrasound removes the polymer microballoon in the solution that can dissolve the polymer microballoon, keeps the main surface exposed
Multiple units of non-mask film covering out.
In another preferred example, the temperature of the pyrolytic is 250~1000 DEG C.
In another preferred example, the heating time of the pyrolytic is 5~60min.
In another preferred example, the polymer microballoon is Properties of Polystyrene Nano Particles, and/or, the soluble polymeric
The solution of object microballoon is toluene solution.
In another preferred example, the step (d) includes:
Retain or all remove the mask layer.
In another preferred example, the mask layer includes: Titanium, chromium, silicon nitride, silica, or combinations thereof.
In another preferred example, the mask layer is silicon nitride.
In another preferred example, pass through the silicon nitride mask layer on substrate described in acid solution erosion removal.
In another preferred example, the acid solution is selected from the group: HCl, HF, H3PO4、HNO3、H2SO4, or combinations thereof.
In another preferred example, in the step (d), the corrosion carries out in alkaline solution.
In another preferred example, the time of the corrosion is 1~1000s.
In another preferred example, the etching time is 180s.
In another preferred example, the alkaline solution is selected from the group: potassium hydroxide/Isopropanol Solvent solution, sodium hydroxide/
Isopropanol Solvent solution, tetramethyl ammonium hydroxide solution, or combinations thereof.
In another preferred example, in the potassium hydroxide/Isopropanol Solvent solution potassium hydroxide mass concentration be 5~
70%.
In another preferred example, in the sodium hydroxide/Isopropanol Solvent solution, the mass concentration of isopropanol is 5~
50%.
In another preferred example, in the tetramethyl ammonium hydroxide solution tetramethylammonium hydroxide mass concentration be 2~
50%.
In another preferred example, the temperature of the alkaline solution is 0~200 DEG C, preferably 20-150 DEG C.
In another preferred example, the mask layer be do not reacted with alkaline solution arbitrarily (or with alkaline solution react speed
Rate is far below monocrystalline silicon) and the substance for being attached to silicon face can be stablized in alkaline solution.
The second aspect of the present invention, provides a kind monocrystalline silicon, and the monocrystalline silicon includes described in first aspect present invention
Preparation method preparation flannelette, the flannelette have inverted pyramid array structure, wherein the inverted pyramid array structure by
Multiple reverse pyramid indent compositions, the average bottom surface side length of shown indent are 10nm~10000nm.
In another preferred example, the monocrystalline silicon includes: p-type solar energy-level silicon wafer, N-type solar energy-level silicon wafer, p-type collection
At circuit level silicon wafer or N-type integrated circuit level silicon wafer.
In another preferred example, the main surface area of the monocrystalline silicon is 0.25cm2~900m2。
Third aspect present invention, provides a kind of solar battery, and the solar battery includes second party of the present invention
Monocrystalline silicon described in face.
It should be understood that above-mentioned each technical characteristic of the invention and having in below (eg embodiment) within the scope of the present invention
It can be combined with each other between each technical characteristic of body description, to form a new or preferred technical solution.As space is limited, exist
This no longer tires out one by one states.
Detailed description of the invention
Fig. 1 is that the process of the monocrystalline silicon inverted pyramid array structure flannelette preparation method in one embodiment of the present invention is shown
It is intended to；
Fig. 2 is scanning electron microscope (SEM) photo in the embodiment of the present invention 1:
The SEM photograph of polystyrene nanospheres (PS ball) film after (2-1) self assembly,
SEM photograph of (2-2,2-3) the inverted pyramid array structure flannelette under different amplification；
Fig. 3 is SEM photo of the inverted pyramid array structure flannelette under different amplification in the embodiment of the present invention 2.
Fig. 4 is to carry out the reflectivity of inverted pyramid array structure making herbs into wool before and after the processing to monocrystalline silicon surface in inventive embodiments
Compare map.
Specific embodiment
The present inventor after extensive and in-depth study, has found for the first time by largely testing, can be by with polymer
Microballoon is that exposure mask prepares inverted pyramid array structure flannelette, the specific surface for the inverted pyramid array structure flannelette that this method is prepared
Product is small, photonic absorption is excellent, and its preparation process is simple, and low in cost, overcoming the prior art can not generate on a large scale, preparation
Condition requires the disadvantages of harsh.In addition, in the present invention, the size of reverse pyramid indent in inverted pyramid array structure flannelette
It can be controlled by adjusting the size of etching time or polymer microballoon.The present invention is completed on this basis.
Inverted pyramid array structure
Inverted pyramid structure of the present invention refers on the surface of monocrystalline silicon, by corrosion generation by periodically ordered row
The suede structure of inverted pyramid indent (reverse pyramid concave surface) composition of column.Wherein, each indent position is polymerization
The distributing position of the contact surface of object microballoon and substrate.When generating mask layer, these contact surfaces are blocked by polymer microballoon, are not had
Mask film covering (becomes the unit for not covering the exposure mask), so can expose the table of substrate after removing polymer microballoon
Face and be corroded.
Monocrystalline silicon
Monocrystalline silicon piece is anisotropic, the corrosion on different crystal orientations when being corroded in the aqueous slkali of a certain concentration range
Rate is different.In the present invention, using this principle, the monocrystalline silicon piece of particular crystal orientation is put into aqueous slkali and is corroded, Ji Ke
Silicon chip surface produces many tiny inverted pyramid shape appearances.
Drift method
Drift method of the present invention refers to the formation 2D polymer microballoon periodic array on air-liquid interfacial, then
The array is transferred on substrate as exposure mask.
Preferably, in an example of the invention, (PS ball) illustrates above method by taking polystyrene spheres as an example: will be from Aladdin
The PS solution (mass fraction 10-20%) and dehydrated alcohol bought at company 1~1.2 mixing by volume, ultrasound 5~
It is stand-by after 12min；By dodecyl sodium sulfate (SDS) be configured to saturated aqueous solution and with 0.1%~1% body ratio participate in from
Sub- aqueous solution is stand-by；It is slowly dropped into the PS ball liquid postponed in deionized water liquid level, can thus form one layer of orderly densification
PS ball film.The diameter of above-mentioned single layer polystyrene nanospheres can be 50nm~1000nm.
The preparation method of monocrystalline silicon inverted pyramid array structure flannelette
The present invention also provides the preparation methods of monocrystalline silicon inverted pyramid array structure flannelette of the present invention.In general, this method
Include:
(1) polymer microballoon single thin film is generated at least one main surface of the substrate, obtains substrate-polymer
Microballoon single thin film；
(2) mask layer is generated on the substrate-polymer microballoon single thin film, obtains substrate-polymer microballoon single layer
Film-mask layer；
(3) polymer microballoon in the substrate-polymer microballoon single thin film-mask layer is removed, the main surface is made
Expose multiple units of non-mask film covering；
(4) unit that corrosion does not cover the exposure mask is reverse pyramid indent, in the main surface of the substrate
Obtain inverted pyramid array structure flannelette.
In a preference of the invention, the preparation of the monocrystalline silicon inverted pyramid array structure flannelette includes following step
It is rapid:
(i) after cleaning silicon chip, substrate is activated using activating agent, obtaining has hydrophilic substrate table
Face；
(ii) polymer nanocomposite ball is carried out using the drift method (floating-transferring) in self-assembling technique
It is self-assembled into single thin film, and film is laid with to substrate；
(iii) the single polymer layer nanosphere for obtaining step (ii) is grown certain thick as exposure mask on this silicon chip
The silicon nitride mask layer of degree；
(iv) the polymer nanocomposite ball on silicon chip is removed, the silicon substrate hexagoinal lattice array junctions that do not protected by silicon nitride are obtained
Structure (array structure of the unit composition of i.e. non-mask film covering layer).
(v) it configures certain density alkaline corrosion liquid and controls temperature and etching time, according to the selection of wet etching
Property, the above-mentioned reverse pyramid indent for not being etched into particular size by the silicon substrate surface that silicon nitride mask layer covers；
(vi) above-mentioned mask layer and cleaning silicon chip are removed with acid corrosion liquid, obtains a nanometer inverted pyramid array structure, completed
The preparation of advanced silicon substrate light trapping structure flannelette.
Using
The flannelette specific surface area that the present invention prepares the inverted pyramid array structure of monocrystalline silicon is small, and photonic absorption ability is complete
It can be matched with the prior art or more than the prior art, can be used for preparing solar battery, optical sensor and LED light etc..
Main advantages of the present invention include:
(1) specific surface area for the inverted pyramid array structure flannelette that method of the invention is prepared is small, photonic absorption ability
It can be matched completely with the prior art, or even more preferable than the effect of the prior art, still, preparation process is simple, and it is low in cost, gram
Having taken the prior art can not generate on a large scale, and preparation condition requires the disadvantages of harsh.
(2) present invention prepares large area, high-quality, size adjustable using polymer microballoon as the lithographic technique of exposure mask
Inverted pyramid array structure flannelette.It is demonstrated experimentally that c-Si inverted pyramid array prepared by the present invention, base diameter can 10~
Regulated and controled between 10000nm.Enhance characteristics such as light absorption, specific surface area be small etc. using it, structure can be applied to optics
In the devices such as senser element, LED light, solar battery.
(3) gap from large to small, has apparent gradually changed refractive index to inverted pyramid structure produced by the present invention from top to bottom
Characteristic, i.e. impedance matching property.The reflection of incident light is effectively suppressed.
(4) of the invention preparation is simple, with existing industrial process good compatibility, is suitable for popularization and application.
Inverted pyramid structure etching method proposed by the present invention has the characteristics that saving substrate, is particularly suitable for ultra-thin solar battery
Using it is blunt can to take into account surface when preparing nanometer inverted pyramid suede structure for the silicon nitride mask layer used in technique
Good sunken optical property can be obtained again by changing, and be advantageous to reduce production cost.
(5) in the present invention, the size of reverse pyramid indent can be rotten by adjusting in inverted pyramid array structure flannelette
The size of erosion time or polymer microballoon is controlled.
(6) in the present invention, using the polymer microballoon single thin film of drift method preparation large area, so that falling golden
Preparing for word tower array structure flannelette is simpler.
Present invention will be further explained below with reference to specific examples.It should be understood that these embodiments are merely to illustrate the present invention
Rather than it limits the scope of the invention.In the following examples, the experimental methods for specific conditions are not specified, usually according to conventional strip
Part or according to the normal condition proposed by manufacturer.Unless otherwise stated, otherwise percentage and number are weight percent and weight
Number.
The embodiment of the present invention is mainly using the orderly polymer nano granules of substrate surface as exposure mask, then in crystalline silicon substrate
Upper deposition silicon substrate mask layer exposure mask removes the polymer nanocomposite ball on silicon wafer, forms list using the wet etching technique of lye
The periodic structure of crystal silicon nanometer inverted pyramid.
Embodiment 1
Monocrystalline silicon inverted pyramid array structure flannelette No.1
As described in Figure 1, the present embodiment prepare monocrystalline silicon inverted pyramid structure flannelette method the following steps are included:
Silicon chip is stand-by through over cleaning, as Figure 1-1；
Polymer nanocomposite ball array is formed using the drift method in self assembly, is then laid on substrate, wherein
Polymer microballoon average diameter can select between 50nm~10000nm, as shown in Figs. 1-2；
Utilize PECVD (Plasma Enhanced Chemical Vapor Deposition, plasma enhanced chemical
Vapour deposition process) method body surface shown in Fig. 1-2 grow one layer of silicon nitride mask layer and protect silicon substrate surface, nitridation
Silicon film thickness is controllable, as shown in Figs. 1-3；
Using the polymer globules on silicon chip in pyrolytic Fig. 1-3, nanometer then is completed using lye wet etching
The forming of inverted pyramid array structure, wherein the bottom side length of inverted pyramid can be regulated and controled by etching time, side size range
It is can be controlled in 50nm~10000nm, periodic lattice size can regulate and control by the diameter of polymer globules, lattice constant control
Range is 50nm~10000nm, as shown in Figs 1-4.
Suitable sour corrosion solvent is selected, removes the nitridation on silicon chip on a small quantity or all by wet etching removal
Then silicon mask layer cleans silicon chip with general cleaning method again, as shown in Figs 1-4.
The embodiment prepares nanometer golden word using 300nm diameter polystyrene bead (PS ball) self assembly periodic array
Tower structure array.
The present embodiment using 200 μ m thicks (100) crystal face c-Si piece, resistivity be 1-10 Ω cm, area be 2 ×
2cm2.Using acetone, alcohol, deionized water, the cleaning to silicon chip is completed in ultrasonic cleaning instrument according to sequencing, often
A cleaning step time is 5~10min；Using the drift method in self assembly, the PS ball of 300nm diameter is completed in deionized water
The self assembly of liquid level, forms the bead film (as shown in Fig. 2-1) of one layer of orderly period arrangement, and film shows indigo plant under strong light
Then color directly clamps above-mentioned silicon chip with tweezers and slowly fishes for film, stand-by after this silicon wafer that dries in the shade naturally；Use plasma
Enhancing chemical vapor deposition (PECVD) is completed to the growth of the silicon nitride mask layer of above-mentioned silicon chip, wherein silicon nitride mask layer
Growth thickness is set as 40nm, and temperature control is at 70 DEG C in growth course；By increasing temperature to 250 DEG C or more, complete to above-mentioned
The decomposition of PS ball in silicon chip；Then using 20% KOH and 15% IPA (isopropanol) (being mass ratio) corrosive liquid come
Corrode above-mentioned silicon chip, to form a nanometer inverted pyramid structure array, etching time 180s；Silicon substrate is cleaned with deionized water
The lye of on piece；Silicon nitride mask layer is removed in ultrasound using 30% nitric acid, the time is 5 minutes；Finally use deionization
Silicon chip water cleaning silicon chip and completed with making herbs into wool is dried with nitrogen.Gained nanometer inverted pyramid array structure flannelette is not
Scheme as shown in Fig. 2-2 and Fig. 2-3 with the SEM under amplification factor.
Embodiment 2:
Monocrystalline silicon inverted pyramid array structure flannelette No.2
As described in Figure 1, the present embodiment prepare monocrystalline silicon inverted pyramid structure flannelette method the following steps are included:
Silicon chip is stand-by through over cleaning, as Figure 1-1；
Polymer nanocomposite ball array is formed using the drift method in self assembly, is then laid on substrate, wherein
Polymer microballoon average diameter can select between 50nm~10000nm, as shown in Figs. 1-2；
One layer of metal Ti mask layer, which is grown, using the surface of method object shown in Fig. 1-2 of d.c. sputtering protects silicon chip
Surface, Ti film thickness is controllable, as shown in Figs. 1-3；
The polymer globules in removal Fig. 1-3 above silicon chip are ultrasonically treated using toluene solution, it is then wet using lye
Method etches a nanometer forming for inverted pyramid array structure, when wherein the bottom side length of inverted pyramid indent can pass through corrosion
Between regulate and control, diameter range can be controlled in 50nm~10000nm, periodic lattice size can by the diameters of polymer globules come
Regulation, lattice constant control range are 50nm~10000nm, as shown in Figs 1-4；
Suitable sour corrosion solvent is selected, removes the nitridation on silicon chip on a small quantity or all by wet etching removal
Then silicon mask layer cleans silicon chip with general cleaning method again, as shown in Figs 1-4.
The embodiment prepares nanometer golden word using 300nm diameter polystyrene bead (PS ball) self assembly periodic array
Tower structure array.
This example is using the c-Si piece of (100) crystal face of 200 μ m thicks, and resistivity is 1-10 Ω cm, and area is 2 × 2cm.
Using acetone, alcohol, deionized water, the cleaning to silicon chip, Mei Geqing are completed in ultrasonic cleaning instrument according to sequencing
Washing Step Time is 5~10min；Using the drift method in self assembly, the PS ball of 300nm diameter is completed in deionized water liquid level
Self assembly, form the bead film with the arrangement of orderly period, film is displayed in blue under strong light, then directly pressed from both sides with tweezers
It lives in state silicon chip and slowly fishes for film, it is stand-by after this silicon chip that dries in the shade naturally；It is completed using sputtering to above-mentioned silicon chip
The growth of Ti mask layer, wherein Ti mask layer growth thickness is set as 70nm, and growth course temperature is controlled in room temperature；By in toluene
Ultrasonic 2 minutes removal PS balls in solution；Then using 20% KOH and 15% IPA (being mass ratio) corrosive liquid come rotten
Above-mentioned silicon chip is lost, to form a nanometer inverted pyramid structure array, etching time 180s；Silicon chip is cleaned with deionized water
Upper lye；10 minutes removal Ti mask layers, time are handled in ultrasound using the hydrofluoric acid of 20% (concentration 40%) volume ratio
It is 5 minutes；The silicon chip for finally cleaning silicon chip using deionized water and being completed with making herbs into wool is dried with nitrogen.Gained nanometer is fallen
SEM photograph of the pyramid array structure flannelette under different amplification is as shown in Figure 3.
Testing example
As shown in figure 4, preparation method preparation inverted pyramid array structure flannelette as described in example 2, making herbs into wool using as preceding
All band reflectivity is 38% (see 4-1 curve in Fig. 4) within the scope of preceding plate silicon polishing face 300nm-1100nm, by surface
After inverted pyramid array structure making herbs into wool processing, which is reduced to 15.6% (see 4-2 curve in Fig. 4).
All references mentioned in the present invention is incorporated herein by reference, independent just as each document
It is incorporated as with reference to such.In addition, it should also be understood that, after reading the above teachings of the present invention, those skilled in the art can
To make various changes or modifications to the present invention, such equivalent forms equally fall within model defined by the application the appended claims
It encloses.
Claims (11)
1. a kind of preparation method of monocrystalline silicon suede, which comprises the steps of:
(a) polymer microballoon single thin film is generated in a main surface of substrate, obtains substrate-polymer microballoon single thin layer
Film；
(b) mask layer is generated on the substrate-polymer microballoon single thin film, obtains substrate-polymer microballoon single thin film-
Mask layer, the mask layer are silicon nitride；
(c) polymer microballoon in the substrate-polymer microballoon single thin film-mask layer is removed, keeps the main surface exposed
Multiple units of non-mask film covering out；
(d) corrosion does not cover the unit of the exposure mask, reverse pyramid indent is formed it into, thus in the master of the substrate
Inverted pyramid array structure flannelette is obtained on surface；
And the step (a) includes:
The polymer microballoon film of the orderly period arrangement of single layer is generated by self-assembling technique；With
The polymer microballoon film is taped against in a main surface of the substrate；
And the step (a) includes:
A surface is provided with hydrophilic substrate；
The polymer microballoon film of the orderly period arrangement of single layer is generated by drift method；
There is hydrophilic substrate to be put into the liquid level floating solution for having polymer microballoon film the surface, passes through liquid level sedimentation
The liquid level for reducing the floating solution for having polymer microballoon film of the liquid level, so that the polymer microballoon film is deposited in advance
The substrate surface placed；
Wherein, the drift method refers to the formation 2D polymer microballoon periodic array on air-liquid interfacial, then by the array
It is transferred on substrate as exposure mask, and the generating mode of the mask layer is plasma activated chemical vapour deposition, using described
The generation temperature that plasma chemical vapor deposition generates the mask layer is 70-80 DEG C.
2. preparation method according to claim 1, which is characterized in that generate institute using the plasma chemical vapor deposition
The generation temperature for stating mask layer is 80 DEG C.
3. preparation method according to claim 1, which is characterized in that generate institute using the plasma chemical vapor deposition
The generation temperature for stating mask layer is 70 DEG C.
4. preparation method according to claim 1, which is characterized in that the preparation method is by the step (a), the step
Suddenly (b), the step (c) and the step (d) form.
5. preparation method according to claim 1, which is characterized in that the polymer microballoon is polymer nanocomposite ball, institute
The diameter for stating polymer nanocomposite ball is 50~1000nm.
6. preparation method according to claim 1, which is characterized in that the diameter of the polymer nanocomposite ball be 200~
700nm。
7. preparation method according to claim 1, which is characterized in that the step (c) the following steps are included:
Polymer microballoon described in pyrolytic makes the main surface expose multiple units of non-mask film covering.
8. preparation method according to claim 1, which is characterized in that the step (c) the following steps are included:
Ultrasound removes the polymer microballoon in the solution that can dissolve the polymer microballoon, exposes the main surface not
Multiple units of mask film covering.
9. preparation method according to claim 1, which is characterized in that the step (d) includes:
Retain or all remove the mask layer.
10. preparation method according to claim 1, which is characterized in that in the step (d), the corrosion is in alkali
It is carried out in property solution.
11. preparation method according to claim 10, which is characterized in that the alkaline solution is selected from the group: potassium hydroxide/
Isopropanol Solvent solution, sodium hydroxide/Isopropanol Solvent solution, tetramethyl ammonium hydroxide solution, or combinations thereof.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910086667.0A CN109881250A (en) | 2014-05-09 | 2014-05-09 | A kind of monocrystalline silicon inverted pyramid array structure flannelette and its preparation method and application |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410196601.4A CN103952768A (en) | 2014-05-09 | 2014-05-09 | Monocrystal silicon inverted pyramid array structure suede, and preparation method and application thereof |
| CN201910086667.0A CN109881250A (en) | 2014-05-09 | 2014-05-09 | A kind of monocrystalline silicon inverted pyramid array structure flannelette and its preparation method and application |
Related Parent Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410196601.4A Division CN103952768A (en) | 2014-05-09 | 2014-05-09 | Monocrystal silicon inverted pyramid array structure suede, and preparation method and application thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN109881250A true CN109881250A (en) | 2019-06-14 |
Family
ID=51330109
Family Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410196601.4A Pending CN103952768A (en) | 2014-05-09 | 2014-05-09 | Monocrystal silicon inverted pyramid array structure suede, and preparation method and application thereof |
| CN201910086667.0A Pending CN109881250A (en) | 2014-05-09 | 2014-05-09 | A kind of monocrystalline silicon inverted pyramid array structure flannelette and its preparation method and application |
Family Applications Before (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410196601.4A Pending CN103952768A (en) | 2014-05-09 | 2014-05-09 | Monocrystal silicon inverted pyramid array structure suede, and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (2) | CN103952768A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114551614A (en) * | 2020-11-24 | 2022-05-27 | 苏州阿特斯阳光电力科技有限公司 | Silicon wafer composite suede manufacturing method and silicon wafer manufactured by same |
| CN115377253A (en) * | 2022-10-26 | 2022-11-22 | 季华实验室 | Preparation method of light trapping structure and light trapping structure |
Families Citing this family (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9502594B2 (en) | 2012-01-19 | 2016-11-22 | Alta Devices, Inc. | Thin-film semiconductor optoelectronic device with textured front and/or back surface prepared from template layer and etching |
| US20150380576A1 (en) | 2010-10-13 | 2015-12-31 | Alta Devices, Inc. | Optoelectronic device with dielectric layer and method of manufacture |
| US20170141256A1 (en) | 2009-10-23 | 2017-05-18 | Alta Devices, Inc. | Multi-junction optoelectronic device with group iv semiconductor as a bottom junction |
| US11271128B2 (en) | 2009-10-23 | 2022-03-08 | Utica Leaseco, Llc | Multi-junction optoelectronic device |
| US11038080B2 (en) | 2012-01-19 | 2021-06-15 | Utica Leaseco, Llc | Thin-film semiconductor optoelectronic device with textured front and/or back surface prepared from etching |
| CN105336797B (en) * | 2014-08-05 | 2018-05-11 | 奥塔装置公司 | Thin film semiconductor's photoelectric device with veining front surface and/or back surface |
| CN104538283A (en) * | 2014-12-18 | 2015-04-22 | 中国科学院高能物理研究所 | Preparation method for inverted pyramid structure on silicon wafer surface |
| CN107881561A (en) * | 2017-10-13 | 2018-04-06 | 南昌大学 | The positive pyramid periodic array structure matte preparation method and applications of monocrystalline silicon |
| CN109581559B (en) * | 2019-01-29 | 2021-02-02 | 香港中文大学（深圳） | Double-grating nano structure composed of four-corner biconical array and preparation method thereof |
| CN111318180B (en) * | 2020-03-16 | 2020-12-08 | 中国人民解放***箭军工程设计研究院 | Preparation method of film material containing oriented carbon nanotubes |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1574225A (en) * | 2003-05-20 | 2005-02-02 | Lg.飞利浦Lcd有限公司 | Method of fabricating polycrystalline silicon and switching device using polycrystalline silicon |
| CN101665231A (en) * | 2009-09-18 | 2010-03-10 | 上海芯敏微***技术有限公司 | Structure of thin film device manufactured by means of double-faced opposite-penetrated corrosion based on (100) silicon chip and method thereof |
| CN102157628A (en) * | 2011-03-22 | 2011-08-17 | 马鞍山优异光伏有限公司 | Method for manufacturing silicon wafer texture |
| CN103112816A (en) * | 2013-01-30 | 2013-05-22 | 中国科学院大学 | Method for preparing pyramid array on monocrystalline silicon substrate |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101582331B (en) * | 2009-05-27 | 2011-01-05 | 彩虹集团公司 | Method for preparing platinum counter electrode of dye-sensitized solar battery with large surface area |
| CN101597786B (en) * | 2009-07-02 | 2012-05-23 | 中国科学院物理研究所 | Device and method for preparing colloidal crystal simple layer film |
| CN101693519B (en) * | 2009-10-21 | 2012-07-25 | 吉林大学 | Process for preparing silicon dioxide nano-cone array |
| CN101866982A (en) * | 2010-05-11 | 2010-10-20 | 电子科技大学 | Method for surface regulation of silicon material for solar cells |
| CN102400227B (en) * | 2011-11-22 | 2013-03-13 | 深圳光启高等理工研究院 | Preparation method for pile face black silicon material |
| CN103050574A (en) * | 2012-12-12 | 2013-04-17 | 浙江大学 | Method for growing silicon base ordered quantum dots by taking polystyrene nanoball as template |
| CN103572373B (en) * | 2013-05-10 | 2015-10-21 | 横店集团东磁股份有限公司 | A kind of monocrystalline silicon wafer alkaline formula leather producing process |
-
2014
- 2014-05-09 CN CN201410196601.4A patent/CN103952768A/en active Pending
- 2014-05-09 CN CN201910086667.0A patent/CN109881250A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1574225A (en) * | 2003-05-20 | 2005-02-02 | Lg.飞利浦Lcd有限公司 | Method of fabricating polycrystalline silicon and switching device using polycrystalline silicon |
| CN101665231A (en) * | 2009-09-18 | 2010-03-10 | 上海芯敏微***技术有限公司 | Structure of thin film device manufactured by means of double-faced opposite-penetrated corrosion based on (100) silicon chip and method thereof |
| CN102157628A (en) * | 2011-03-22 | 2011-08-17 | 马鞍山优异光伏有限公司 | Method for manufacturing silicon wafer texture |
| CN103112816A (en) * | 2013-01-30 | 2013-05-22 | 中国科学院大学 | Method for preparing pyramid array on monocrystalline silicon substrate |
Non-Patent Citations (1)
| Title |
|---|
| 张济忠等编著: "《现代薄膜技术》", 31 January 2009 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114551614A (en) * | 2020-11-24 | 2022-05-27 | 苏州阿特斯阳光电力科技有限公司 | Silicon wafer composite suede manufacturing method and silicon wafer manufactured by same |
| CN115377253A (en) * | 2022-10-26 | 2022-11-22 | 季华实验室 | Preparation method of light trapping structure and light trapping structure |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103952768A (en) | 2014-07-30 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109881250A (en) | A kind of monocrystalline silicon inverted pyramid array structure flannelette and its preparation method and application | |
| CN103956395B (en) | Array structure matte and its preparation method and application | |
| Liu et al. | Hierarchical robust textured structures for large scale self-cleaning black silicon solar cells | |
| CN102157628B (en) | Method for manufacturing silicon wafer texture | |
| Lv et al. | Porous-pyramids structured silicon surface with low reflectance over a broad band by electrochemical etching | |
| TW200620441A (en) | Method for manufacturing semiconductor substrate, semiconductor substrate for solar cell and etching solution | |
| CN103579416B (en) | A kind of preparation method with inverted pyramid structure template | |
| CN101877362B (en) | Silicon substrate with period structure | |
| CN102270688A (en) | Solar cell | |
| US20090071532A1 (en) | Solar cell and fabricating method thereof | |
| CN102593261A (en) | Silicon substrate nano-structure for solar cell and preparing method thereof | |
| US20140319524A1 (en) | Substrates having a broadband antireflection layer and methods of forming a broadband antireflection layer | |
| CN104576813B (en) | A kind of nanostructured matte on photoelectric material surface and preparation method thereof | |
| CN104143496A (en) | Crystalline silicon film manufacturing method based on layer transferring | |
| Kayabasi et al. | Determination of micro sized texturing and nano sized etching procedure to enhance optical properties of n-type single crystalline silicon wafer | |
| CN103979485A (en) | Preparation method of micro nano porous silicon material | |
| CN104124286B (en) | A kind of utilization growth noble metals certainly etc. are from primitive nanostructured | |
| Thiyagu et al. | Ultra-low reflectance, high absorption microcrystalline silicon nanostalagmite | |
| CN104310304A (en) | Preparation method of nano column array with controllable size and surface structure | |
| Nichkalo et al. | Fabrication and characterization of high-performance anti-reflecting nanotextured Si surfaces for solar cells | |
| CN102400227A (en) | Preparation method for pile face black silicon material | |
| CN102154712A (en) | Monocrystal silicon solar battery texture etching liquid and preparation method thereof | |
| Moona et al. | Silicon wafer surface reflectance investigations by using different surface texturing parameters | |
| KR20160146126A (en) | Method for texturing of semiconductor substrate, semiconductor substrate manufactured by the method and solar cell comprising the same | |
| Huang et al. | Fabrication of novel hybrid antireflection structures for solar cells |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20190614 |