CN106920744B - Method for stimulating diffusion of non-metal atoms in silicon in room temperature environment - Google Patents
Method for stimulating diffusion of non-metal atoms in silicon in room temperature environment Download PDFInfo
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- CN106920744B CN106920744B CN201510994328.4A CN201510994328A CN106920744B CN 106920744 B CN106920744 B CN 106920744B CN 201510994328 A CN201510994328 A CN 201510994328A CN 106920744 B CN106920744 B CN 106920744B
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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
Abstract
The invention discloses a method for exciting diffusion of non-metal impurity atoms in silicon. Under the room temperature environment, the silicon material or the silicon device is processed by Inductively Coupled Plasma (ICP), so that the diffusion of non-metal atoms such As P, B, As, O, N, F and the like in the silicon can be stimulated. The method has the advantages of no need of high temperature, convenience, rapidness, low cost and low secondary pollution degree, can be used for improving the performance of the silicon material, and can be used for improving the performance of the device after the silicon device is manufactured.
Description
Technical Field
the invention relates to a diffusion technology of non-metal atoms in silicon materials, in particular to a method for exciting the diffusion of the non-metal atoms in the silicon under a room temperature environment.
Background
The silicon material inevitably contains non-metallic elements such as carbon, oxygen, nitrogen, etc. The nonmetal impurities have important influence on the device properties of the silicon material, for example, oxygen precipitates in the silicon have the function of internal impurity absorption and can block the external diffusion of transition metals; the formation of oxygen-boron recombination pairs can combine with photons in a silicon solar cell to cause a light decay phenomenon, thereby reducing the efficiency of the cell. Impurity atoms such as phosphorus and arsenic are introduced into a silicon material to play a role of shallow donors in silicon, and impurity atoms such as boron are introduced to play a role of shallow acceptors. The concentration distribution changes of arsenic, boron and the like in silicon caused by diffusion have important influence on the performance of silicon materials and devices.
Diffusion of impurity atoms in single crystal silicon typically requires high temperatures of seven, eight hundred or even thousands of degrees celsius and a long time, and not only is the procedure complicated and costly, but also it is vulnerable to contamination by impurities from the surrounding environment during heating, and in the case of silicon devices, the high temperature diffusion method also causes severe degradation of device performance.
Disclosure of Invention
The invention aims to provide a simple and convenient method for exciting the diffusion of non-metal impurity atoms in silicon under the ambient condition of room temperature rather than high temperature.
The technical scheme of the invention is as follows:
A method for exciting non-metal impurity atoms in silicon to diffuse is to carry out Inductively Coupled Plasma (ICP) processing on silicon materials or silicon devices in a room temperature environment.
experiments prove that the ICP can stimulate non-metal atoms such As P, B, As, O, N, F and the like in silicon to diffuse.
The carrier gas for ICP treatment is an inert gas such as helium and the degree of vacuum is at least 1E-2Pa, usually around 5E-3 Pa.
Furthermore, the power of ICP treatment is 10-10000W, preferably 50-1000W, and more preferably 100-750W; the treatment time is 30sec to 60min, preferably 1min to 10 min.
the silicon material includes silicon wafers, but is not limited to silicon wafers.
The invention stimulates the diffusion of non-metal impurity atoms in silicon by ICP, and the possible principle is as follows:
During ICP processing, a radio frequency power supply is energized to deliver energy through an induction coil to the gas within the reaction chamber to ionize it, form a plasma, and produce a glow. The electron temperature in the plasma is very high and can reach 2000-10000K. Positive ions and electrons in the plasma strike the wafer surface, resulting in a surface defect zone and a large number of elementary point defects: a vacancy defect V. This is the motive force to drive the diffusion of impurity atoms.
Non-metallic impurity atoms that are easily oxidized, such as B, P, As, exist in silicon in combination with oxygen to form impurity-oxygen atom pairs (I-O). Vacancies V released by vacancy-type defects generated by ICP move to the vicinity of an I-O atom pair, depriving it of O, forming a V-O pair, as shown in equation (1):
V+I-O→V-O+I (1)
the substitutional or interstitial diffusion coefficient of the reduced non-metallic impurity atoms I is generally much greater than that of I-O.
On the other hand, the substitutional diffusion coefficient D of impurity atoms in siliconsThere is the formula:
In the formula (2), a is a geometric factor and is determined by a crystal structure; v. of0Is the frequency of vibration, EVIndicates the vicinity of impurity atomsEnergy required for the formation of vacancies, ESIndicating that the atom moving to an adjacent vacancy requires a potential barrier across the domains.
Since ICP generates a large amount of V released from vacancy type defects, vacancies easily occur in the vicinity of non-metallic impurity atoms, which means EVIt is significantly reduced and the diffusion coefficient is exponentially increased. Whether easily oxidizable non-metallic impurity atoms such as B, P, As or O, N, F reduced by vacancies exist mainly in substitutional form in silicon, the substitutional diffusion coefficient is significantly increased by the large number of vacancies generated by ICP, and thus room temperature diffusion is possible.
Because ICP causes a large number of vacancy type defects on the surface of the silicon wafer, part of the non-metallic impurity atoms can enter these vacancy type defects, reducing their surface concentration, allowing the non-metallic impurity atoms in the bulk to diffuse toward the surface. In conclusion, the distribution of the non-metallic impurity elements in the silicon can be changed at room temperature by using the technical method.
The method of the invention utilizes the inductive coupling plasma with larger power to process the silicon chip, so that the non-metal impurities in the silicon are excited and diffused in the room temperature environment. The method is realized in the room temperature environment, so the method not only can be used for improving the performance of the silicon material, but also can be used for diffusing non-metal impurity atoms in the device at room temperature after the silicon device is manufactured so as to improve the performance of the device.
Drawings
FIG. 1: and the distribution of As atomic concentration along with depth of the P-type solar-grade silicon single crystal wafer after the ICP treatment of 750W for 2 minutes.
FIG. 2: and F atom concentration distribution of the P-type solar-grade silicon single crystal wafer after ICP treatment of 750W for 2 minutes is shown.
FIG. 3: the distribution of B atom concentration with depth of the P type solar grade silicon single crystal wafer after 750W ICP processing for 2 minutes is shown.
Detailed Description
The invention is further illustrated by the following examples, which are not intended to limit the scope of the invention in any way.
Example 1:
A P-type solar-grade Czochralski silicon single crystal wafer is selected, and is polished on one side, the resistivity is 1.9 omega cm, and the thickness is 625 mu m. Firstly, ultrasonic cleaning is respectively carried out on a monocrystalline silicon piece for 10min by using acetone, ethanol and deionized water. Then immersing the silicon wafer into 2 percent HF solution to remove a natural oxidation layer on the surface of the silicon wafer. And performing ICP treatment on the polished surface of the silicon wafer, wherein the carrier gas is helium, the flow rate is 22sccm, the vacuum degree is about 5E-3Pa, the treatment time is 2min, and the power is 750W. And finally, measuring the distribution of As impurity atom concentration in the silicon wafer sample along with the depth by using an SIMS means. As can be seen from FIG. 1, the As concentration on the surface of the silicon wafer was from 1E19atoms/cm3Increased to 1E21atoms/cm3The increase of the surface As concentration shows that the diffusion speed of As impurity atoms at room temperature is obviously enhanced, and ICP irradiation can stimulate the diffusion of As in silicon at room temperature.
Example 2:
A P-type solar-grade Czochralski silicon single crystal wafer is selected, and is polished on one side, the resistivity is 1.9 omega cm, and the thickness is 625 mu m. Firstly, ultrasonic cleaning is respectively carried out on a monocrystalline silicon piece for 10min by using acetone, ethanol and deionized water. Then immersing the silicon wafer into 2 percent HF solution to remove a natural oxidation layer on the surface of the silicon wafer. And performing ICP treatment on the polished surface of the silicon wafer, wherein the carrier gas is helium, the flow rate is 22sccm, the vacuum degree is about 5E-3Pa, the treatment time is 2min, and the power is 750W. And finally, measuring the distribution of the O element impurity concentration in the silicon wafer sample along with the depth by using an SIMS (simple independent modeling system) method. As can be seen from FIG. 2, the concentration of O on the surface of the silicon wafer was from 1E19atoms/cm3Increased to 1E21atoms/cm3The increase of the surface F concentration shows that the diffusion speed of O impurity atoms at room temperature is obviously enhanced, and ICP irradiation can stimulate the diffusion of O in silicon at room temperature.
example 3:
A P-type solar-grade Czochralski silicon single crystal wafer is selected, and is polished on one side, the resistivity is 1.9 omega cm, and the thickness is 625 mu m. Firstly, ultrasonic cleaning is respectively carried out on a monocrystalline silicon piece for 10min by using acetone, ethanol and deionized water. Then immersing the silicon wafer into 2 percent HF solution to remove a natural oxidation layer on the surface of the silicon wafer. Then polishing the surface of the silicon waferPerforming ICP treatment with helium as carrier gas, flow rate of 22sccm, vacuum degree of 5E-3Pa or so, treatment time of 2min and power of 750W. And finally, measuring the distribution of the B element impurity concentration in the silicon wafer sample along with the depth by using an SIMS (simple independent modeling system) method. As can be seen from FIG. 3, the concentration of B on the surface of the silicon wafer was from 1E18atoms/cm3Increased to 1E19atoms/cm3The diffusion speed of B impurity atoms at room temperature is obviously enhanced due to the increase of the surface B concentration, and the diffusion of B in silicon at room temperature can be stimulated by ICP irradiation.
Claims (9)
1. A method for exciting non-metal impurity atoms in silicon to diffuse is characterized in that inductively coupled plasma processing is carried out on a silicon material or a silicon device under a room temperature environment.
2. the method of claim 1, wherein the carrier gas for the inductively coupled plasma process is an inert gas and the vacuum is at least 1E-2 Pa.
3. The method of claim 2 wherein the carrier gas for the inductively coupled plasma process is helium.
4. The method of claim 1, wherein the inductively coupled plasma process has a power of 10 to 10000W.
5. The method of claim 4, wherein the inductively coupled plasma processing is performed at a power of 50W to 1000W.
6. The method of claim 5, wherein the inductively coupled plasma process has a power of 100W to 750W.
7. The method of claim 1, wherein the inductively coupled plasma treatment time is 30sec to 60 min.
8. The method of claim 7, wherein the inductively coupled plasma processing time is 1min to 10 min.
9. The method of any one of claims 1 to 8, wherein the non-metallic impurity atoms comprise one or more of P, B, As, O, N and F.
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Effective date of registration: 20230925 Address after: 100176 Beijing Daxing District Beijing economic and Technological Development Zone Wenchang Road 8 Patentee after: BEIJING NAURA MICROELECTRONICS EQUIPMENT Co.,Ltd. Address before: 100871 No. 5, Yiheyuan Road, Haidian District, Beijing Patentee before: Peking University |