碳化硅宽带隙半导体材料生长技术及应用

出处:zab 发布于:2007-04-29 10:30:33

王强,李玉国,石礼伟,孙海波
(山东师范大学半导体研究所,山东 济南 250014)
摘要:概括了宽带隙半导体材料碳化硅的主要特性及生长方法,介绍了其在微电子光电子领域的应用,并对其发展动态及存在问题进行了简要评述。

关键词:宽带隙半导体;碳化硅;光电子学

1 Introduction

As it is well known,the traditional Si and GaAs devices are inapplicable at the temperature above 250 ℃,and they cannot perform well under the conditions of high frequency,high power and strong radiation. When compared with Si and GaAs,SiC material has many advantages,such as wide bandgap,high breakdown field,high thermal conductivity,high saturated drift velocity of electrons,stable chemical properties and survival ability in strong radiation,which make it a promising candidate in the adverse circumstance where the silicon devices have been disabled. Taking the advantage of its wide bandgap(23 eV~33 eV),the blue,green and ultraviolet lightemitting devices and photo detectors have been fabricated. What is more,a naturally formed thin layer of SiO2 on its surface is advantageous to the devices based on SiC MOS,which is unique,when compared with other compounds such as GaN and AlN,etc.

Nowadays the studies of SiC are mainly focused on the crystalline growth and the formation of thin films of 4HSiC,6HSiC,3CSiC,and the investigation of SiC devices have also gained much concern in recent years. In this article,the progresses of SiC are discussed,and the existing problems are appraised and commented.

2The basicproperties of SiC

2.1The semiconductor properties of SiC

SiC material has extraordinary thermal stability and chemical stability. There is no dopant diffusion at any rational temperature. At room temperature,it can endure any acid etching. Other excellent properties of SiC are showed in Table 1.

2.2 Poly types of SiC

The structure of SiC is tetragonal(Fig.1). The bonding of Si and C atom is rather strong,but the bonding between the layers is comparatively weak,therefore SiC has more than 200 polytypes. According to the crystal phases of SiC,they can be sorted into three kinds,they are,cubic,hexagonal and rhombohedral phases. The thick stacking has three different positions,which are labeled A,B and C. Depending on the sequence of stacking,SiC crystals will have cubic zincblende structure or hexagonal wurtzite structure. For example,if the stacking sequence is ABCABC...,we will obtain cubic zincblende structure,which is labeled as 3CSiC(or βSiC),while the sequence is ABAB...,we will get wurtzite structure,which is labeled 2HSiC. Other polytypes,such as 4HSiC and 6HSiC are the mixture of the above two kinds of stacking(Fig.2). Different polytypes show the same chemical properties,but they have different physical properties,especially in respect of semiconductor properties. Heterostructure and superlattice of SiC polytypes with entirely matched crystal lattice have been made into SiC devices with excellent performance,utilizing those of the above properties of SiC.

3 The prearation of SiC

3.1 The growth of bulk crystal

A majority of semiconductor crystals can be prepared in their melted state or in solution. But SiC cannot be melted under traditional condition,and it cannot be prepared in any solutions until now. The Acheson Method is the earliest method to form SiC crystal. In the year of 1955,Lely used the sublimation method(without seed crystal)to form 3CSiC with pin shape. From the late 70 s to the early 80 s of last century,Tairov and Tsvetkov improved the Lely Method,and realized the seeded sublimation of SiC.

3.1.1SiC prepared by Acheson Method

For a long time,the growth of SiC bulk crystal had been the bottleneck of the application of SiC in the field of electronics. In the early years,people used the Acheson Method to form SiC(Fig.3). Silica and carbon were mixed and reacted at the temperature above 2500 ℃,so someone said that,“Silicon carbide is born in fire”. The carborundum(SiC)formed by Acheson Method is mainly used as materials for abrasion and cutting,but it can also be used as electronic material for rather low requirement. Due to such disadvantages as high growth temperature and poor crystal quality,it is being replaced by subsequent techniques such as Lely Method,modified Lely Method and CVD epitaxy method.

3.1.2 SiC prepared by the Lely Method and the modified Lely Method

The crystal SiC formed by Lely Method(Fig.4)has greatly improved crystal quality,but its growth rate is rather low,and the type of the crystal cannot be controlled. Nowadays SiC formed by this method is usually used as substrate to obtain high quality epitaxial crystal. From the 80 s of last century,the Sublimation method(modified Lely Method(Fig.5)),which is also called Physical Vapor Transport Method(PVT),has been employed to grow SiC crystal,and it has been the predominant method for SiC production. But the growth temperature is still high(above 2100 ℃),large amount of micropipes and high density of dislocations exist in the crystal. and the control of the type of the crystal is difficult. Until the 90 s of the last century,the fabrication technique had been greatly improved,and the 4HSiC and 6HSiC wafers with low density of micropipe defects(10~100 micropipes/cm2)had been obtained. The doping of SiC is often in the process of its growth,and the ntype SiC is doped by nitrogen,while the ptype is doped by aluminum. The doping after growth is often realized by the ion implantation technology,and the common diffusion method cannot get high doping concentration. Due to the nitrogen gas ambience in the growth process,the unintentionally doped SiC is of n type. Nowadays there are four companies who can provide commercialized SiC wafers,that is,CREE Research Inc.(USA),Nippon Steel(Japan),AT MI Corp.(USA),SiCrystal AG(Germany),and the SiC wafers are mostly prepared by the sublimation method.

3.2 The growth of SiC thin film

Due to the difference of the substrate,there are two different epitaxy methods to form SiC thin film,they are,homoepitaxy and heteroepitaxy. Because of the large mismatch of the lattices(about 20%)and the large difference of the thermal expansion coefficients(about 8%),large amount of dislocations and stresses will be introduced in during the growth process. Before epitaxy,the silicon subasrate is usually carbonized at first to form a thin buffer layer. Then high quality epilayer of SiC will be obtained on it. Because of the commercialization of SiC wafers with rather big size,the homoepitaxy of SiC has developed rapidly,especially the techniques of stepcontrolled epitaxy and sitecompetition epitaxy. The methods to form SiC thin film include sputtering,laser ablation,sublimation epitaxy,liquid phase epitaxy(LPE),chemical vapor deposition(CVD),molecular beam epitaxy(MBE),electron cyclotron resonance chemical vapor deposition(ECRCVD)and metal organic chemical vapor deposition(MOCVD). The cool wall CVD method(Fig.6)is the most successful one. The precursors(often SiH4,C3H8 and CH4)are transported by hydrogen to the hot zone where the reaction takes place. During the reaction,C3H8 is introduced firstly to form the buffer layer,then SiH4 is introduced also,and the temperature is kept at about 1300 ℃,subsequently the thin film of SiC is formed. The growth rate is rather low,usually several μm/h. Afterwards the Hot Wall CVD method had been introduced,and the growth rate had been increased to 05 mm/h,while the control of the growth condition became difficult.

4 The investigation of SiC devices

Due to the breakthrough of the growth technology of SiC crystal and its thin film,SiC devices have been extensively investigated in recent years. The applications of 4HSiC and 6HSiC devices in the fields of high frequency,high temperature,high power and optoelectronics are shown in Table 2.

5 Conclusion and prospects

In the latest decades,much strive has been contributed to the study of SiC,and great breakthrough has been gained. The size of SiC wafers has been increased year by year,the Φ75 cm wafers have been put into market,and the Φ10 cm wafers have been successfully formed in labs. The quality of SiC wafers is also improved year by year,the micropipe defects of the Φ5 cm wafers has been reduced to <10/cm2,while those of the Φ25 cm wafer have been eliminated.

There are still many technical problems needing to be solved to sufficiently explore the potential applications of SiC,which include:(1)the epitaxy mechanism of SiC thin film is not so clear;(2)3CSiC can only be obtained by heteroepitaxy,therefore there are kinds of defects that cannot be eliminated;(3)some key techniques such as etching,oxidization,ohmic contact and package,are not so mature;(4)duo to its instinct indirect bandgap structure,the application of SiC in the field of optoelectronics has been severely handicapped.

本文摘自《微纳电子技术》

  
关键词:半导体

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