CN109326504A - A kind of preparation method of bandgap tunable high conductivity silicon-based thin film - Google Patents
A kind of preparation method of bandgap tunable high conductivity silicon-based thin film Download PDFInfo
- Publication number
- CN109326504A CN109326504A CN201810959326.5A CN201810959326A CN109326504A CN 109326504 A CN109326504 A CN 109326504A CN 201810959326 A CN201810959326 A CN 201810959326A CN 109326504 A CN109326504 A CN 109326504A
- Authority
- CN
- China
- Prior art keywords
- gas flow
- silicon
- film
- preparation
- substrate
- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02104—Forming layers
- H01L21/02365—Forming inorganic semiconducting materials on a substrate
- H01L21/02367—Substrates
- H01L21/0237—Materials
- H01L21/02373—Group 14 semiconducting materials
- H01L21/02381—Silicon, silicon germanium, germanium
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02104—Forming layers
- H01L21/02365—Forming inorganic semiconducting materials on a substrate
- H01L21/02518—Deposited layers
- H01L21/02521—Materials
- H01L21/02524—Group 14 semiconducting materials
- H01L21/02529—Silicon carbide
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02104—Forming layers
- H01L21/02365—Forming inorganic semiconducting materials on a substrate
- H01L21/02518—Deposited layers
- H01L21/0257—Doping during depositing
- H01L21/02584—Delta-doping
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02104—Forming layers
- H01L21/02365—Forming inorganic semiconducting materials on a substrate
- H01L21/02612—Formation types
- H01L21/02617—Deposition types
- H01L21/0262—Reduction or decomposition of gaseous compounds, e.g. CVD
Landscapes
- Engineering & Computer Science (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Manufacturing & Machinery (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Photovoltaic Devices (AREA)
Abstract
A kind of preparation method of band gap adjustable height conductivity silica-base film, using quartzy and monocrystalline silicon as substrate, one layer of phosphorus doping amorphous Silicon-rich SiC film is grown using plasma reinforced chemical vapour deposition (PECVD), passes through feed change gas methane (CH4), silane (SiH4) and suitable phosphine (PH3) gas flow, realize C/Si ratio adjusting and doping concentration change；Wherein CH4/SiH4The proportional region of gas flow is 0.3~3, PH3Gas flow variation be 0sccm~80sccm；By annealing, Amorphous GaN film is made to obtain crystallization, forms the silicon nanocrystal being embedded in Amorphous GaN film.SiH4Gas flow 1sccm or more, PH30.5~80sccm or more of gas flow.
Description
Technical field
The present invention relates to the designs and preparation of a kind of doping silicon nanocrystal based on silicon substrate and quartz substrate material.Especially
Be the matrix material for relating to the use of SiC as silicon nanocrystal, the conductivity of film improved by adulterating, obtain band gap and
The adjustable silica-base film of electric conductivity is applied to semiconductor silicon base optical electronic and nanometer electronic device.
Background technique
In recent years, the silicon nanocrystal being embedded in insulating materials has potential application prospect in photoelectric device, can be by
As next-generation solar battery, luminescent device, nonvolatile storage and detector etc., arouse widespread concern.
Generally, insulating materials SiO2It can be used to the matrix material as silicon nanocrystal, this composite material of formation has good
Good photoelectric properties, have greatly widened the application range of this kind of material.Meanwhile SiO2It, can with good passivation
The recombination probability for efficiently reducing carrier improves the performance of device.In addition to this, SiO2It is also used as the silicon of multilayer film
Deielectric-coating serves as limitation crystallization layer.But SiO2The forbidden bandwidth of material is larger, inlays in silica even if preparing
Nanometer silicon composite material, conductivity is still lower, is unfavorable for the tunnelling of carrier, transports and collect, limits it in light
Further applying in electrical part.
Relative to SiO2, Amorphous GaN as a kind of silica-base material have smaller optical band gap, the shape between silicon materials
At valence band and conduction band potential barrier offset it is smaller, be conducive to improve carrier tunneling efficiency and improve corresponding device property
Energy.And the size of its optical band gap can be adjusted by C/Si ratio, and there are good impurity activations under annealing conditions
Effect.But its conductivity of the adjustable SiC material of band gap is often lower；Using SiC as the matrix material of silicon nanocrystal
Material, the C/Si for changing film compare band gap and are regulated and controled；The conductivity that film is improved by adulterating, obtains band gap and electric conductivity
Adjustable silica-base film is applied in semiconductor silicon base optical electronic and nanometer electronic device, develops high performance semiconductor light electrical chip
Meaningful work.
The present invention carries out the high temperature anneal to the Silicon-rich SiC film of amorphous, and film obtains crystallization, forms and be embedded in
The composite material of silicon nanocrystal in SiC, compared to unannealed Amorphous GaN film, conductivity is had been improved, and has reached 1.2
×10-6S/cm, but its conductivity is still too low.In order to further increase the conductivity of this composite material, we receive silicon
Rice crystalline substance is adulterated, it is found that the conductivity of this composite material is greatly improved.Meanwhile by annealing technology, make
Amorphous GaN film obtains crystallization, forms the silicon nanocrystal being embedded in Amorphous GaN, and the size of mobility obviously increases, changes
It has been apt to the transport capability of carrier, has improved the electric property of this composite material.Therefore, the SiC of band gap adjustable height conductance is thin
Film can be used as the Window layer of solar battery or the transport layer of silicon-based photoelectric device.In addition, similar technology can also develop
It uses in silicon-rich silicon nitride silicon fiml (SiNx).
Summary of the invention
Object of the present invention is to using SiC as the matrix material of silicon nanocrystal, by changing the C/ in SiC film
Si ratio and annealing temperature achieve the purpose that adjust its optical band gap.It is right meanwhile in order to further increase the conductivity of material
Silicon nanocrystal has carried out the doping of various concentration.
The technical scheme is that a kind of preparation method of band gap adjustable height conductivity silica-base film, basic characteristics are
Using quartz and monocrystalline silicon as substrate, it is rich that one layer of phosphorus doping amorphous is grown using plasma reinforced chemical vapour deposition (PECVD)
Silicon SiC film (by annealing technology, makes Amorphous GaN film obtain crystallization, forms the silicon nanometer being embedded in Amorphous GaN film
It is brilliant), by changing methane (CH4), silane (SiH4) and phosphine (PH3) gas flow, realize C/Si ratio adjusting and mix
The change of miscellaneous concentration.Wherein CH4/SiH4Proportional region be 0.3~3, PH3Gas flow variation be 0sccm~80sccm.
Especially SiH4Gas flow 1sccm or more, PH30.5~80sccm or more of gas flow (P- silicon raw material).
Typical implementation steps are as follows:
1) quartz and p-Si cleaned up is as substrate；
2) silicon substrate and quartz substrate after cleaning are put into growth amorphous Silicon-rich SiC film in PECVD chamber；
3) dehydrogenation and annealing are carried out in tube furnace, in tube furnace N2450 ± 5 DEG C of guarantors are carried out in protective atmosphere respectively
60 ± 5min or 1000 ± 5 DEG C of 60 ± 5min of heat preservation of warm 60 ± 5min and 900 ± 5 DEG C of heat preservation；
4) the Al electrode of four angle vapor deposition planars of quartz substrate；
5) alloying Al film, in tube furnace N2425 ± 5 DEG C of 30 ± 5min of heat preservation in protective atmosphere；
6) transmission spectrum and reflectance spectrum of film are measured, and combines Tauc formula, calculates the optical band gap of sample；
7) conductivity of vanderburg method measurement film；
8) for the film grown on silicon substrate after step 3) processing, the Al electrode of planar, front vapor deposition is deposited in the back side
The Al electrode of pectination；Obtain the schematic diagram of the product structure such as Fig. 5；
9) after step 5) processing, the photovoltaic property of device is tested.
The invention has the advantages that: (one) by changing annealing temperature and C/Si ratio, realizes to silica-base film material
The regulation of optical band gap, the variation range of optical band gap are 1.8eV~2.7eV；
(2) by changing the doping concentration of amorphous Silicon-rich SiC, the conductivity of silica-base film material, conductivity are improved
It can reach 760S/cm.C/Si by changing film compares band gap and is regulated and controled；The conductance of film is improved by adulterating
Rate, obtains band gap and the adjustable silica-base film of electric conductivity is applied in semiconductor silicon base optical electronic and nanometer electronic device, and development is high
The semiconductor light electrical chip of performance.
Detailed description of the invention
Fig. 1 preparation flow figure provided by the invention；
Fig. 2 is CH4=5sccm, SiH4=5sccm and PH3The SiC film of=50sccm throughput growth, 900 DEG C of annealing
Raman scattering figure afterwards, the size of silicon nanocrystal are 5.4nm；
Fig. 3 is SiH4=5sccm and PH3=3sccm changes CH4Gas flow be respectively 1.5sccm, 2.5sccm and
5sccm, the variation of Film Optics band gap；
Fig. 4 is SiH4=5sscm, CH4=1.5sccm changes PH3Gas flow be respectively 0sccm, 0.5sccm,
1.1sccm and 5sccm, the variation of film conductivity；
Fig. 5 battery device schematic diagram provided by the invention；
The J-V curve of Fig. 6 Si NCs:SiC provided by the invention and a-SiC heterojunction solar battery.
Specific embodiment
To make the objectives, technical solutions, and advantages of the present invention clearer, below in conjunction with specific embodiment, to this hair
It is bright to be further described.The present invention provides the preparation flow schematic diagrames of band gap adjustable height conductivity silicon substrate, as shown in Figure 1.
(1) gas flow of thin-film material is respectively as follows: CH4=5sccm, SiH4=5sccm and PH3=50sccm.By
900 DEG C of annealings, sample obtain crystallization, form the silicon nanocrystal being embedded in Amorphous GaN film, and size is
5.4nm, as shown in Figure 2.
(2) in order to regulate and control to carbon silicon ratio, SiH4And PH3Gas flow be fixed as 5sccm and 3 sccm, CH4Gas
Body flow changes into 1.5sccm, 2.5sccm and 5sccm.With the variation of silicon carbon ratio, optical band gap also occurs to change accordingly.
As shown in Figure 3.
(3) thin-film material of different levels of doping in order to obtain, CH4And SiH4Gas flow be fixed as 1.5 sccm and
5sccm, PH3Gas flow change into 0sccm, 0.5sccm, 1.1sccm and 5sccm.Form the thin-film material of silicon nanocrystal
Conductivity, occur to change accordingly with the variation of doping concentration.The conductivity of its thin-film material can reach 760S/
cm.As shown in Figure 4.
Example 1:
(4) phosphorus being embedded in Amorphous GaN film prepared mixes Window layer of the silicon nanocrystal as heterojunction solar battery,
Device architecture is as shown in Figure 5.
(5) using the efficiency of solar cell photoelectric transfer efficiency test macro measurement battery, the uniformity of radiant light exists
Within ± 2%, light-intensity variation is below ± 1%.Fig. 6 is the illumination J-V based on annealing both front and back heterojunction solar battery
Curve.Wherein the gas flow of thin-film material is respectively as follows: CH4=5sccm, SiH4=5sccm and PH3=50sccm.It is original heavy
Open-circuit voltage, short-circuit current density and the fill factor of long-pending heterojunction solar battery are respectively 352mV, 14.39mA/
cm2With 36.3%, the photoelectric conversion efficiency of battery is 1.84%.Based on the Si NCs:SiC heterojunction solar battery after annealing
Performance obviously improved.Its open-circuit voltage, short-circuit current density and fill factor increased respectively to 548mV,
24.07mA/cm2With 38.9%, photoelectric conversion efficiency has also been increased to 5.56%.
Particular embodiments described above has carried out further in detail the purpose of the present invention, technical scheme and beneficial effects
It describes in detail bright, it should be understood that the above is only a specific embodiment of the present invention, is not intended to restrict the invention, it is all
Within the spirit and principles in the present invention, any modification, equivalent substitution, improvement and etc. done should be included in guarantor of the invention
Within the scope of shield.
Claims (4)
1. a kind of preparation method of band gap adjustable height conductivity silica-base film, characterized in that using quartzy and monocrystalline silicon as substrate,
One layer of phosphorus doping amorphous Silicon-rich SiC film is grown using plasma reinforced chemical vapour deposition (PECVD), passes through feed change gas
The gas flow of methane (CH4), silane (SiH4) and suitable phosphine (PH3) realizes the adjusting and doping concentration of C/Si ratio
Change；The variation of gas flow that wherein proportional region of CH4/SiH4 gas flow is 0.3~3, PH3 be 0sccm~
80sccm；By annealing, Amorphous GaN film is made to obtain crystallization, forms the silicon nanocrystal being embedded in Amorphous GaN film.
2. preparation method according to claim 1, characterized in that be SiH4 gas flow 1sccm or more, the gas of PH3
0.5~80sccm or more of flow.
3. preparation method according to claim 2, characterized in that implementation steps are as follows:
1) quartz and p-Si cleaned up is as substrate；
2) silicon substrate and quartz substrate after cleaning are put into growth amorphous Silicon-rich SiC film in PECVD chamber；
3) dehydrogenation and annealing are carried out in tube furnace, carried out respectively in tube furnace N2 protective atmosphere 450 ± 5 DEG C of heat preservations 60 ±
60 ± 5min or 1000 ± 5 DEG C of 60 ± 5min of heat preservation of 5min and 900 ± 5 DEG C of heat preservation.
4. preparation method according to claim 2, characterized in that gas flow, that is, doping concentration variation of PH3 and make
The conductivity of thin-film material reaches 760S/cm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810959326.5A CN109326504A (en) | 2018-08-22 | 2018-08-22 | A kind of preparation method of bandgap tunable high conductivity silicon-based thin film |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810959326.5A CN109326504A (en) | 2018-08-22 | 2018-08-22 | A kind of preparation method of bandgap tunable high conductivity silicon-based thin film |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN109326504A true CN109326504A (en) | 2019-02-12 |
Family
ID=65263580
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810959326.5A Pending CN109326504A (en) | 2018-08-22 | 2018-08-22 | A kind of preparation method of bandgap tunable high conductivity silicon-based thin film |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109326504A (en) |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7795120B1 (en) * | 2009-08-28 | 2010-09-14 | The United States Of America As Represented By The Secretary Of The Navy | Doping wide band gap semiconductors |
| CN102280545A (en) * | 2011-08-17 | 2011-12-14 | 中国科学院苏州纳米技术与纳米仿生研究所 | Silicon-based light emission device and method for making same |
| CN103000742A (en) * | 2012-12-04 | 2013-03-27 | 南京大学 | Solar battery with band gap gradual changing silicon quantum dot multilayer film and production method thereof |
-
2018
- 2018-08-22 CN CN201810959326.5A patent/CN109326504A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7795120B1 (en) * | 2009-08-28 | 2010-09-14 | The United States Of America As Represented By The Secretary Of The Navy | Doping wide band gap semiconductors |
| CN102280545A (en) * | 2011-08-17 | 2011-12-14 | 中国科学院苏州纳米技术与纳米仿生研究所 | Silicon-based light emission device and method for making same |
| CN103000742A (en) * | 2012-12-04 | 2013-03-27 | 南京大学 | Solar battery with band gap gradual changing silicon quantum dot multilayer film and production method thereof |
Non-Patent Citations (3)
| Title |
|---|
| JI, Y ET AL.: "Formation of high conductive nano-crystalline silicon embedded in amorphous silicon-carbide films with large optical band gap", 《AIP ADVANCES》 * |
| SHAN, D ET AL.: "Microstructure and carrier-transport behaviors of nanocrystalline silicon thin films annealed at various temperatures", 《PHYSICA STATUS SOLIDI A-APPLICATIONS AND MATERIALS SCIENCE》 * |
| 季阳等: "镶嵌于非晶碳化硅中的高导电性掺杂纳米晶硅的制备与电学性能研究", 《南京大学学报(自然科学)》 * |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Prathap et al. | Thin film silicon solar cells by AIC on foreign substrates | |
| Krishna et al. | Solar cells based on carbon thin films | |
| Dornstetter et al. | Deposition of high-efficiency microcrystalline silicon solar cells using SiF 4/H 2/Ar mixtures | |
| JP2692091B2 (en) | Silicon carbide semiconductor film and method for manufacturing the same | |
| Miyajima et al. | Highly conductive microcrystalline silicon carbide films deposited by the hot wire cell method and its application to amorphous silicon solar cells | |
| CN101694853A (en) | ZnO/SiC/Si heterojunction solar battery and preparation method thereof | |
| EP0053402B1 (en) | Pin photovoltaic cell having a hetero junction of amorphous siliconcompound and amorphous silicon | |
| Wang et al. | Heteroepitaxial growth of Cu2O films on Nb-SrTiO3 substrates and their photovoltaic properties | |
| Matsumoto et al. | Performance of p-type silicon-oxide windows in amorphous silicon solar cell | |
| Myong et al. | Low-temperature preparation of boron-doped nanocrystalline SiC: H films using mercury-sensitized photo-CVD technique | |
| Konagai et al. | High-rate deposition of silicon thin-film solar cells by the hot-wire cell method | |
| Hamashita et al. | Preparation of Al-doped hydrogenated nanocrystalline cubic silicon carbide by VHF-PECVD for heterojunction emitter of n-type crystalline silicon solar cells | |
| CN109326504A (en) | A kind of preparation method of bandgap tunable high conductivity silicon-based thin film | |
| Liu et al. | Enhanced device performance of Si nanowires/Si nanocrystals heterojunction solar cells with ultrathin Al2O3 passivation | |
| Hao et al. | Structure, stability and photoelectronic properties of transition films from amorphous to microcrystalline silicon | |
| You et al. | Hydrogen-rich c-Si interfacial modification to obtain efficient passivation for silicon heterojunction solar cell | |
| Huang et al. | Preparation of microcrystalline silicon solar cells on microcrystalline silicon carbide window layers grown with HWCVD at low temperature | |
| Das et al. | Development of oxide based window and buffer layer for single junction amorphous solar cell: Reduction of light induced degradation | |
| Ambrosone et al. | Microcrystalline silicon thin films grown at high deposition rate by PECVD | |
| Das et al. | Development of highly conducting p-type μc-Si: H films from minor diborane doping in highly hydrogenated SiH4 plasma | |
| Focsa et al. | Heterojunction a-Si/poly-Si solar cells on mullite substrates | |
| Ma et al. | Microstructure and photoelectric properties of P-doped silicon-rich SiNx film as an n-type layer for PIN-type amorphous silicon thin film solar cells | |
| Matsui et al. | Doping properties of boron-doped microcrystalline silicon from B2H6 and BF3: material properties and solar cell performance | |
| Yoshinaga et al. | Fabrication of silicon and carbon based wide-gap semiconductor thin films for high conversion efficiency | |
| JPS62268128A (en) | Manufacture of microcrystal silicon carbide film |
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 |
Application publication date: 20190212 |
|
| RJ01 | Rejection of invention patent application after publication |