CN104425241A - Method for removing natural oxide layer - Google Patents

Method for removing natural oxide layer Download PDF

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Publication number
CN104425241A
CN104425241A CN201310409612.1A CN201310409612A CN104425241A CN 104425241 A CN104425241 A CN 104425241A CN 201310409612 A CN201310409612 A CN 201310409612A CN 104425241 A CN104425241 A CN 104425241A
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CN
China
Prior art keywords
oxidizing layer
natural oxidizing
minimizing technology
layer according
germanium
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
Application number
CN201310409612.1A
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Chinese (zh)
Inventor
王桂磊
赵超
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Institute of Microelectronics of CAS
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Institute of Microelectronics of CAS
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Filing date
Publication date
Application filed by Institute of Microelectronics of CAS filed Critical Institute of Microelectronics of CAS
Priority to CN201310409612.1A priority Critical patent/CN104425241A/en
Publication of CN104425241A publication Critical patent/CN104425241A/en
Pending legal-status Critical Current

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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
    • H01L21/04—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
    • H01L21/31—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to form insulating layers thereon, e.g. for masking or by using photolithographic techniques; After treatment of these layers; Selection of materials for these layers
    • H01L21/3105—After-treatment
    • H01L21/311—Etching the insulating layers by chemical or physical means
    • H01L21/31105—Etching inorganic layers
    • H01L21/31111—Etching inorganic layers by chemical means
    • H01L21/31116—Etching inorganic layers by chemical means by dry-etching

Abstract

The invention provides a method for removing a natural oxide layer. The natural oxide layer formed on the surface of a semiconductor substrate is removed by using hydride of germanium at temperature of 400 to 600 DEG C. The method for removing the natural oxide layer, provided by the invention, is low in treatment temperature, loss of silicon of the semiconductor substrate can be effectively avoided, the overall removal process can be performed in epitaxial reaction equipment, and chambers of the epitaxial reaction equipment do not to be modified, so the treatment cost can be greatly lowered as well.

Description

A kind of minimizing technology of natural oxidizing layer
Technical field
The present invention relates to field of semiconductor device preparation, particularly a kind of method removing natural oxidizing layer before extension.
Background technology
Epitaxy technique is conventional one growth SiGe, the method of the strain gauge materials such as Ge, SiC, GeSn, in order to go out strain (strain) material in the superficial growth of Semiconductor substrate, before epitaxy technique, first need the silicon dioxide natural oxidizing layer (native oxide) removing semiconductor substrate surface.The method of removal natural oxidizing layer conventional is at present hydrofluoric acid aftertreatment technology (HF-last), namely hydrofluoric acid is used to erode the natural oxidizing layer of semiconductor substrate surface, remaining of the natural oxidizing layer that 1nm is thick but the semiconductor substrate surface after usually using hydrofluoric acid treatment complete is still had an appointment, and if do not enter vacuum reaction cavity in time, the thickness of natural oxidizing layer also can be thickening because of oxidation, therefore also need to remove residual natural oxidizing layer by front baking process (Pre Baking) or low temperature plasma bombardment etching process in extension reaction chamber.
The treatment temperature of front baking process is generally greater than 750 DEG C, for high-K gate dielectric and metal gate (HKMG, High k metal gate) extension of integrated and three-dimensional fin transistor (Finfet3D), easily cause the loss of the substrate silicon material exposed, and then affect the performance of semiconductor device, and for advanced process device, the front baking process of high temperature needs lower heat budget (thermbudget); Damage (PID, the Plasma Induce damage) problem that low-temperature plasma bombardment etching process easily brings plasma to cause, and the volume increasing epitaxial device is needed because needing to set up a cavity, cause the operating cost of equipment also higher.
Summary of the invention
In view of this, the invention provides a kind for the treatment of temperature low, the minimizing technology of the natural oxidizing layer that cost is low.
For achieving the above object, the minimizing technology of natural oxidizing layer provided by the invention is under the temperature conditions of 400 DEG C ~ 600 DEG C, uses the natural oxidizing layer on the hydride removal semiconductor substrate surface of germanium.
The hydride of the germanium in method provided by the invention easily decomposes at a certain temperature, and the germanium decomposited and natural oxidizing layer (composition is silicon dioxide) reaction generate volatile germanium monoxide and silicon monoxide, thus are effectively removed by natural oxidizing layer.
In a preferred embodiment of the invention, the general formula of the hydride of described germanium is Ge nh 2n+2, wherein n is 1,2 or 3, includes first germane (GeH in above-mentioned general formula 4), digermane (Ge 2h 6) and three germane (Ge 3h 8), for first germane, in the process removing natural oxidizing layer, there is following reaction:
GeH 4→Ge+2H 2↑；
Ge+SiO 2→GeO↑+SiO↑。
In a preferred embodiment of the invention, use the natural oxidizing layer on gaseous mixture removal semiconductor substrate surface, described gaseous mixture comprises hydride and the hydrogen of germanium, under the carrying of hydrogen, the hydride of germanium more easily enters consersion unit, and can also byproduct of reaction be taken away, in addition, hydrogen possesses very strong reproducibility, can suppress the formation of semiconductor substrate surface oxide layer.
More preferably, in described gaseous mixture, the hydride of germanium and the volume ratio of hydrogen are (1 ~ 10): 100.
More preferably, the flow of described gaseous mixture is 20SCCM ~ 500SCCM.
More preferably, the duration of ventilation of described gaseous mixture is 10s ~ 300s.
In a preferred embodiment of the invention, in the process removing natural oxidizing layer, also pass into hydrogen, its flow is 20SLM ~ 180SLM.Logical hydrogen is conducive to taking away byproduct of reaction, and hydrogen possesses very strong reproducibility, can suppress the formation of semiconductor substrate surface oxide layer further.
In a preferred embodiment of the invention, the process removing natural oxidizing layer is carried out under the condition of 20Torr ~ 760Torr.
In another preferred embodiment of the invention, remove in the process of natural oxidizing layer and also can pass into chlorine or hydrogen chloride gas, it can pass into consersion unit together with the hydride of germanium, also chlorine or hydrogen chloride gas can be passed into again after the hydride of germanium passes into end, when the object done like this is to prevent the hydride of germanium excessive, have excessive germanium deposit on the surface of a semiconductor substrate, its process of specifically reacting is as follows:
Ge+4HCl→GeCl 4↑+H 2↑。
More preferably, the flow of described chlorine or hydrogen chloride gas is 20SCCM ~ 1000SCCM.
The treatment temperature of the minimizing technology of natural oxidizing layer provided by the invention is low, effectively can avoid the loss of semiconductor device substrates silicon, and whole removal process can be carried out in extension consersion unit, do not need to carry out any transformation to the chamber of extension consersion unit, therefore processing cost also reduces greatly.
Accompanying drawing explanation
Fig. 1 is high-resolution X-ray diffraction (HR-XRD) collection of illustrative plates removing the semiconductor substrate surface epitaxial loayer after natural oxidizing layer through the method disclosed in the present.
Embodiment
For enabling above-mentioned purpose, the feature and advantage of invention more become apparent, below the specific embodiment of the present invention is described in detail.
Set forth a lot of detail in the following description so that fully understand the present invention, but the present invention can also adopt other to be different from alternate manner described here to implement, those skilled in the art can when without prejudice to doing similar popularization when intension of the present invention, therefore the present invention is by the restriction of following public specific embodiment.
Raw material used in embodiments of the invention is as follows:
First germane gaseous mixture: the percent by volume of first germane is 10%, and all the other are hydrogen, Air Product air chemical company
Hydrogen: High Purity Hydrogen, Air Product air chemical company
Hydrogen chloride gas: Lin De special gas company
The present invention's reactor used is as follows:
The model that Xian Jing Semiconductor Co., Ltd of the U.S. produces is the rpcvd equipment (RPCVD) of ASM E2000
The present invention's tester used is as follows:
The model that Jodran valley company of Britain produces is the high-resolution X-ray diffractometer (HR-XRD) of Q3;
The model that ATOMIKA company produces is the ion microprobe (SIMS) of SIMS4500.
Embodiment 1
After prerinse is carried out to the reaction chamber of rpcvd equipment, Semiconductor substrate through HF-last process is put into reaction chamber, 600 DEG C, under the condition of 125Torr, in reaction chamber, pass into first germane gaseous mixture, the hydrogen of 120SLM and the hydrogen chloride gas of 200SCCM that flow is 200SCCM simultaneously, stop passing into first germane gaseous mixture and hydrogen chloride gas after 125s, and keep the flow of hydrogen constant, now namely obtain high-quality not containing the Semiconductor substrate of natural oxidizing layer; Then in same reaction chamber, epitaxial growth process can be carried out to Semiconductor substrate according to demand, namely can obtain the semiconductor device of band strain film.
As shown in Figure 1, epitaxial loayer is SiGe strain gauge material, occurs obvious interference fringe in the both sides at SiGe peak, shows that the interface cohesion of SiGe and Si is better, does not have the residual of natural oxidizing layer.
By the C of the interface of sims analysis Semiconductor substrate and epitaxial loayer, O content is at 1E18at/cm 3below, show that the natural oxidizing layer in Semiconductor substrate is removed clean.
Although the present invention is described in conjunction with above embodiment, but the present invention is not defined to above-described embodiment, and only by the restriction of claims, those of ordinary skill in the art can easily modify to it and change, but do not leave essential idea of the present invention and scope.

Claims (10)

1. a minimizing technology for natural oxidizing layer, is characterized in that, under the temperature conditions of 400 DEG C ~ 600 DEG C, uses the natural oxidizing layer on the hydride removal semiconductor substrate surface of germanium.
2. the minimizing technology of natural oxidizing layer according to claim 1, is characterized in that, the general formula of the hydride of described germanium is Ge nh 2n+2, wherein n is 1,2 or 3.
3. the minimizing technology of natural oxidizing layer according to claim 1, is characterized in that, use the natural oxidizing layer on gaseous mixture removal semiconductor substrate surface, described gaseous mixture comprises hydride and the hydrogen of germanium.
4. the minimizing technology of natural oxidizing layer according to claim 3, is characterized in that, in described gaseous mixture, the hydride of germanium and the volume ratio of hydrogen are (1 ~ 10): 100.
5. the minimizing technology of natural oxidizing layer according to claim 3, is characterized in that, the flow of described gaseous mixture is 20SCCM ~ 500SCCM.
6. the minimizing technology of natural oxidizing layer according to claim 3, is characterized in that, the duration of ventilation of described gaseous mixture is 10s ~ 300s.
7. the minimizing technology of natural oxidizing layer according to claim 1, is characterized in that, in the process removing natural oxidizing layer, also pass into hydrogen, its flow is 20SLM ~ 180SLM.
8. the minimizing technology of natural oxidizing layer according to claim 1, is characterized in that, the process removing natural oxidizing layer is carried out under the condition of 20Torr ~ 760Torr.
9. the minimizing technology of natural oxidizing layer according to claim 1, is characterized in that, removes in the process of natural oxidizing layer and also passes into chlorine or hydrogen chloride gas.
10. the minimizing technology of natural oxidizing layer according to claim 8, is characterized in that, the flow of described chlorine or hydrogen chloride gas is 20SCCM ~ 1000SCCM.
CN201310409612.1A 2013-09-10 2013-09-10 Method for removing natural oxide layer Pending CN104425241A (en)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106257631A (en) * 2015-06-18 2016-12-28 中芯国际集成电路制造(上海)有限公司 A kind of semiconductor device and manufacture method, electronic installation
CN109119331A (en) * 2017-06-23 2019-01-01 上海新昇半导体科技有限公司 A kind of semiconductor devices and its manufacturing method, electronic device
CN115132570A (en) * 2022-09-01 2022-09-30 睿力集成电路有限公司 Processing method and device for semiconductor structure

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CN101191251A (en) * 2006-11-20 2008-06-04 上海华虹Nec电子有限公司 Method for removing natural oxidizing layer before silicon chip low-temperature epitaxy growth
CN101355016A (en) * 2007-07-23 2009-01-28 东部高科股份有限公司 Method for cleaning semiconductor device
CN102206799A (en) * 2011-04-20 2011-10-05 北京大学 Surface passivation method for germanium-based MOS (Metal Oxide Semiconductor) device substrate
US20120241815A1 (en) * 2011-03-23 2012-09-27 Samsung Electronics Co., Ltd Semiconductor devices and methods of fabricating the same

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101191251A (en) * 2006-11-20 2008-06-04 上海华虹Nec电子有限公司 Method for removing natural oxidizing layer before silicon chip low-temperature epitaxy growth
CN101355016A (en) * 2007-07-23 2009-01-28 东部高科股份有限公司 Method for cleaning semiconductor device
US20120241815A1 (en) * 2011-03-23 2012-09-27 Samsung Electronics Co., Ltd Semiconductor devices and methods of fabricating the same
CN102206799A (en) * 2011-04-20 2011-10-05 北京大学 Surface passivation method for germanium-based MOS (Metal Oxide Semiconductor) device substrate

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Title
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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106257631A (en) * 2015-06-18 2016-12-28 中芯国际集成电路制造(上海)有限公司 A kind of semiconductor device and manufacture method, electronic installation
CN109119331A (en) * 2017-06-23 2019-01-01 上海新昇半导体科技有限公司 A kind of semiconductor devices and its manufacturing method, electronic device
TWI658178B (en) * 2017-06-23 2019-05-01 上海新昇半導體科技有限公司 A semiconductor device, the method of making the same and an electronic device
CN109119331B (en) * 2017-06-23 2021-02-02 上海新昇半导体科技有限公司 Semiconductor device, manufacturing method thereof and electronic device
CN115132570A (en) * 2022-09-01 2022-09-30 睿力集成电路有限公司 Processing method and device for semiconductor structure

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Application publication date: 20150318