CN106920744A - A kind of method that non-metallic atom diffusion in silicon is encouraged in room temperature environment - Google Patents

A kind of method that non-metallic atom diffusion in silicon is encouraged in room temperature environment Download PDF

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Publication number
CN106920744A
CN106920744A CN201510994328.4A CN201510994328A CN106920744A CN 106920744 A CN106920744 A CN 106920744A CN 201510994328 A CN201510994328 A CN 201510994328A CN 106920744 A CN106920744 A CN 106920744A
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silicon
coupled plasma
inductively coupled
room temperature
plasma treatment
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CN106920744B (en
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秦国刚
谢兮兮
侯瑞祥
李磊
徐万劲
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Beijing Naura Microelectronics Equipment Co Ltd
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Peking University
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    • 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
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer
    • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic System or AIIIBV compounds with or without impurities, e.g. doping materials
    • H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
    • H01L21/322—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to modify their internal properties, e.g. to produce internal imperfections

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  • 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)
  • Crystals, And After-Treatments Of Crystals (AREA)
  • Silicon Compounds (AREA)

Abstract

The invention discloses a kind of method for encouraging nonmetallic inclusion atoms permeating in silicon.Under room temperature environment, silicon materials or silicon device are carried out with inductively coupled plasma (ICP) treatment, the non-metallic atom such as P, B, As, O, N, F in silicon can be encouraged to spread.The method is convenient and swift without high temperature, with low cost, by secondary pollution degree far beyond high temperature for small, cannot be only used for improving the performance of silicon materials, the performance of device after silicon device completes, can also be improved with the method.

Description

A kind of method that non-metallic atom diffusion in silicon is encouraged in room temperature environment
Technical field
The present invention relates to the diffusion technique of non-metallic atom in silicon materials, nonmetallic original in more particularly to encouraging silicon under room temperature environment The method of son diffusion.
Background technology
Inevitably contain the nonmetalloids such as carbon, oxygen, nitrogen in silicon materials.Device of these nonmetallic inclusions to silicon materials Matter has a major impact, and such as Oxygen in silicon precipitation plays the role of intrinsic gettering, can hinder the external diffusion of transition metal；Oxygen-boron it is compound to shape Into, can be combined with photon in silicon solar cell and be caused light decay phenomenon, reduce battery efficiency.Phosphorus, arsenic are introduced in silicon materials Deng foreign atom, shallow donor is played in silicon, and introduce the foreign atoms such as boron, play shallow acceptor effect.Caused by diffusion Arsenic and the distribution of boron isoconcentration change in silicon, and the performance of silicon materials and device will be had a major impact.
Foreign atom spreads in monocrystalline silicon generally needs high temperature and some time of seven, 800 or even thousands of degrees Celsius, not only journey Sequence complexity is with high costs, and staining for the impurity from surrounding environment is highly susceptible in heating process, for silicon device, High temperature diffusion process also results in device performance and seriously degenerates.
The content of the invention
It is an object of the invention to provide it is a kind of it is simple and convenient encourage silicon under the environmental condition of room temperature and non high temperature in it is nonmetallic miscellaneous The method of matter atoms permeating.
Technical scheme is as follows：
Silicon materials or silicon device under room temperature environment, are carried out electricity by a kind of method of nonmetallic inclusion atoms permeating in excitation silicon Sense coupled plasma (Inductively Coupled Plasma, hereinafter referred to as ICP) treatment.
It is demonstrated experimentally that ICP can encourage the non-metallic atom such as P, B, As, O, N, F in silicon to spread.
The carrier gas of ICP treatment is inert gas, and such as helium, vacuum is at least 1E-2Pa, generally in 5E-3Pa or so.
Further, the power of ICP treatment is 10~10000W, more preferably preferably 50~1000W, 100~750W；Place The reason time is 30sec~60min, preferably 1min~10min.
The silicon materials include silicon wafer, but are not limited to silicon wafer.
The present invention encourages diffusion of the nonmetallic inclusion atom in silicon by ICP, and its possible principle is as follows：
In ICP processing procedures, the gas that excitation radio-frequency power supply is given the energy in reative cell by induction coil is allowed to ionize, Plasma is formed, and produces aura.Electron temperature is very high in the plasma, up to 2000-10000K.In plasma Cation and electronic impact silicon chip surface, cause surface defect area, and generate a large amount of basic point defects：Vacancy defect V. This is the motive power for driving foreign atom diffusion.
Oxidizable nonmetallic inclusion atom, such as B, P, As, impurity-oxygen atom is combined to form to (I-O) in silicon with oxygen In the presence of.The room V that the vacancy-like defects that ICP is produced are discharged is moved near I-O atom pairs, captures its O, forms V-O It is right, such as shown in reaction equation (1)：
V+I-O→V-O+I (1)
The nonmetallic inclusion atom I being reduced subrogate or interstitial diffusion coefficient typically all much larger than I-O diffusion coefficient.
On the other hand, foreign atom subrogates diffusion coefficient D in siliconsThere is formula：
A is geometrical factor in formula (2), is determined by crystal structure；v0It is vibration frequency, EVRepresent that foreign atom is formed about Energy required for room, ESRepresent that the atom moves adjacent to room and needs cross-domain potential barrier.
By the V that the ICP a large amount of vacancy-like defects of generation are discharged, it is easy to room occur near nonmetallic inclusion atom, this meaning Taste EVCan be obviously reduced, so that diffusion coefficient exponentially rank increase.B, P, As for either being reduced by room etc. is oxidizable Nonmetallic inclusion atom, or the not oxidizable nonmetallic inclusion atom such as O, N, F, it is main to subrogate form presence in silicon, In the presence of a large amount of rooms that ICP is produced, it subrogates diffusion coefficient can significantly increase, consequently, it is possible to realizing that room temperature spreads.
Because ICP causes a large amount of vacancy-like defects in silicon wafer surface, part nonmetallic inclusion atom can lack into these room types Fall into, reduce its surface concentration so that internal nonmetallic inclusion atom is diffused to the surface.In a word, can be using this technology method Change distribution of the nonmetallic inclusion element in silicon under room temperature condition.
The inventive method processes silicon chip using relatively high power inductively coupled plasma so that nonmetallic inclusion is in room temperature environment in silicon Lower to be energized diffusion, this method is convenient and swift without high temperature, with low cost, is small far beyond high temperature by the degree of secondary pollution. Because the inventive method is realized under room temperature environment, so, cannot be only used for improving the performance of silicon materials, can also be in silicon device After completing, nonmetallic inclusion atom room temperature spreads in making device with the method, to improve the performance of device.
Brief description of the drawings
Fig. 1：P-type solar energy level silicon single crystal piece 750W ICP process 2 minutes after, As atomic concentrations with depth distribution Variation diagram.
Fig. 2：After the ICP of 750W is processed 2 minutes, F atom concentration becomes p-type solar energy level silicon single crystal piece with the distribution of depth Change figure.
Fig. 3：After the ICP of 750W is processed 2 minutes, B atomic concentrations become p-type solar energy level silicon single crystal piece with the distribution of depth Change figure.
Specific embodiment
With reference to embodiment, the invention will be further described, the scope of but do not limit the invention in any way.
Embodiment 1：
From p-type solar level czochralski silicon monocrystal disk, single-sided polishing, the Ω cm of resistivity 1.9,625 μm of thickness.First will Monocrystalline silicon piece carries out ultrasonic cleaning 10min respectively with acetone, ethanol, deionized water.It is then immersed in 2% HF solution removal silicon The natural oxidizing layer on piece surface.Then the burnishing surface to silicon chip carries out ICP treatment, and carrier gas is helium, flow 22sccm, vacuum Degree 5E-3Pa or so, process time 2min, power is 750W.Finally with As impurity in SIMS means measurement silicon chip sample Atomic concentration with depth distribution.From figure 1 it appears that the concentration of silicon wafer surface As is from 1E19atoms/cm3Rise to 1E21atoms/cm3, surface A s concentration increases explanation As foreign atoms diffusion velocity at room temperature and significantly increases, ICP Irradiation can encourage diffusions of the As under room temperature environment in silicon.
Embodiment 2：
From p-type solar level czochralski silicon monocrystal disk, single-sided polishing, the Ω cm of resistivity 1.9,625 μm of thickness.First will Monocrystalline silicon piece carries out ultrasonic cleaning 10min respectively with acetone, ethanol, deionized water.It is then immersed in 2% HF solution removal silicon The natural oxidizing layer on piece surface.Then the burnishing surface to silicon chip carries out ICP treatment, and carrier gas is helium, flow 22sccm, vacuum Degree 5E-3Pa or so, process time 2min, power is 750W.O elements are miscellaneous in finally measuring silicon chip sample with SIMS means Matter concentration with depth distribution.From figure 2 it can be seen that the concentration of silicon wafer surface O is from 1E19atoms/cm3Rise to 1E21atoms/cm3, F concentration in surface increases explanation O foreign atoms diffusion velocity at room temperature and significantly increases, ICP irradiation Diffusions of the O under room temperature environment in silicon can be encouraged.
Embodiment 3：
From p-type solar level czochralski silicon monocrystal disk, single-sided polishing, the Ω cm of resistivity 1.9,625 μm of thickness.First will Monocrystalline silicon piece carries out ultrasonic cleaning 10min respectively with acetone, ethanol, deionized water.It is then immersed in 2% HF solution removal silicon The natural oxidizing layer on piece surface.Then the burnishing surface to silicon chip carries out ICP treatment, and carrier gas is helium, flow 22sccm, vacuum Degree 5E-3Pa or so, process time 2min, power is 750W.B element is miscellaneous in finally measuring silicon chip sample with SIMS means Matter concentration with depth distribution.From figure 3, it can be seen that the concentration of silicon wafer surface B is from 1E18atoms/cm3Rise to 1E19atoms/cm3, an order of magnitude is improve, surface B concentration increases explanation B foreign atoms diffusion velocity at room temperature and shows Enhancing is write, ICP irradiation can encourage diffusions of the B under room temperature environment in silicon.

Claims (9)

1. it is a kind of encourage silicon in nonmetallic inclusion atoms permeating method, it is characterised in that under room temperature environment, to silicon materials or silicon Device carries out inductively coupled plasma treatment.
2. the method for claim 1, it is characterised in that carry out the carrier gas of inductively coupled plasma treatment for inert gas, Vacuum is at least 1E-2Pa.
3. method as claimed in claim 2, it is characterised in that the carrier gas for carrying out inductively coupled plasma treatment is helium.
4. the method for claim 1, it is characterised in that the power of the inductively coupled plasma treatment is 10~10000W.
5. method as claimed in claim 4, it is characterised in that the power of the inductively coupled plasma treatment is 50~1000W.
6. method as claimed in claim 5, it is characterised in that the power of the inductively coupled plasma treatment is 100~750W.
7. the method for claim 1, it is characterised in that the time of the inductively coupled plasma treatment is 30sec~60min.
8. method as claimed in claim 7, it is characterised in that the time of the inductively coupled plasma treatment is 1min~10min.
9. the method as described in claim 1~8 any one, it is characterised in that the nonmetallic inclusion atom include P, B, As, One or more in O, N and F.
CN201510994328.4A 2015-12-25 2015-12-25 Method for stimulating diffusion of non-metal atoms in silicon in room temperature environment Active CN106920744B (en)

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Citations (4)

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US20110256724A1 (en) * 2010-04-15 2011-10-20 Novellus Systems, Inc. Gas and liquid injection methods and apparatus
WO2011130326A3 (en) * 2010-04-15 2011-12-15 Novellus Systems, Inc. Plasma activated conformal film deposition
CN102832111A (en) * 2012-09-06 2012-12-19 北京大学 Method for increasing conversion efficiency of solar cell
CN104882377A (en) * 2015-04-21 2015-09-02 北京大学 Method of sucking and removing metal impurity in silicon material at room temperature

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20110256724A1 (en) * 2010-04-15 2011-10-20 Novellus Systems, Inc. Gas and liquid injection methods and apparatus
WO2011130326A3 (en) * 2010-04-15 2011-12-15 Novellus Systems, Inc. Plasma activated conformal film deposition
CN102832111A (en) * 2012-09-06 2012-12-19 北京大学 Method for increasing conversion efficiency of solar cell
CN104882377A (en) * 2015-04-21 2015-09-02 北京大学 Method of sucking and removing metal impurity in silicon material at room temperature

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
LAIXIANG QIN: "Room-temperature diffusion and gettering of Au in silicon stimulated by MeV electron irradiation", 《JOURNAL OF PHYSICS D:APPLIED PHYSICS》 *
YUZHANG: "Gamma-ray irradiation hardness of arrayed silicon microhole-based radical p-n junction solar cells", 《JOURNAL OF PHYSICS D:APPLIED PHYSICS》 *

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