CN102509734A - Method for preparing Ge-based MOS (metal-oxide semiconductor) capacitor by using ALD (atomic layer deposition) - Google Patents
Method for preparing Ge-based MOS (metal-oxide semiconductor) capacitor by using ALD (atomic layer deposition) Download PDFInfo
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- CN102509734A CN102509734A CN2011103489001A CN201110348900A CN102509734A CN 102509734 A CN102509734 A CN 102509734A CN 2011103489001 A CN2011103489001 A CN 2011103489001A CN 201110348900 A CN201110348900 A CN 201110348900A CN 102509734 A CN102509734 A CN 102509734A
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Abstract
The invention belongs to the technical field of semiconductors, and specifically relates to a method for preparing a Ge-based MOS (metal-oxide semiconductor) capacitor by using ALD (atomic layer deposition). The method disclosed by the invention comprises the following steps of: firstly, performing rapid thermal oxidization treatment on a Ge-based substrate to form GeO2; secondly, depositing high-dielectric-constant HfO2 on the GeO2 to serve as a gate dielectric; and finally, manufacturing an electrode to form the Ge-based MOS capacitor. According to the method disclosed by the invention, a layer of high-quality GeO2 is formed on the surface of the Ge-based substrate by adopting a rapid thermal oxidization treatment method, so that Ge can be prevented from diffusing, defect charges and the density of interface state are reduced, and the interface characteristics are improved; and the deposited HfO2 dielectric layer is accurately-controllable in thickness, excellent in conformality, strong in interface controllability and good in uniformity. By adoption of the method disclosed by the invention, the electrical properties of the Ge-based MOS capacitor can be greatly improved, and then the performance of a Ge-based MOS transistor is improved.
Description
Technical field
The invention belongs to technical field of semiconductors, be specifically related to the method that a kind of ALD of utilization makes germanium base mos capacitance.
Background technology
Since the sixties in 20th century, silicon is most important semi-conducting material in the hyundai electronics industry always, mainly is to be used for surface passivation because it forms very high-quality native oxide.Through the lasting miniaturization in more than 40 years, classical body silicon MOSFET just dwindled near its many basic limits, and this just needs the innovation of new material and new device architecture.
High-k (k) material can relax k/3.9 doubly to the restriction of medium physical thickness; Its research in the si-substrate integrated circuit field has obtained many progress; Intel Company has been applied to high-k gate dielectric material and metal gate in the middle of the CPU manufacturing technology of its 45 nm node, has obtained excellent performance.But it also is faced with some problems, like the mass ratio SiO at oxide and interface
2Far short of what is expected, owing to reasons such as Coulomb scattering, phon scatterings, cause the following degradation of channel mobility.
Because (electron mobility is about twice to big many of the mobility ratio silicon of semiconductor Germanium (Ge); Hole mobility is about 4 times); Can relax MOSFET drain current saturation problem, and compatible mutually with traditional si-substrate integrated circuit technology, so germanium is considered to very promising raceway groove alternate material.
Recently, many high-k gate dielectrics are applied on the Ge base MOS, for example aluminium oxide, hafnium oxide, zirconia etc.They reduce the grid leakage current reducing equivalent oxide thickness (EOT), and aspects such as increase hole mobility are very potential.But the mobility in hole does not increase by four times than silicon materials, and the mobility of electronics is not significant yet to be promoted, and possibly mainly be to cause because the interface that gate medium and Ge semiconductor surface form lacks perfection or interface state density is too high.
In addition, development also is the focus of microelectronics research with the compatible mutually film preparing technology of modern CMOS technology.Wherein (Atomic Layer Deposition ALD) is a kind of chemical vapor deposition techniques that can carry out dust () the rank control in other words of monoatomic layer rank to film thickness to the atomic layer deposition technology.The ALD technology has obtained remarkable progress so far from the development seventies in last century, and it has write into international semiconductor technology path figure (ITRS), as demonstrating wide application prospect with the compatible candidate technologies of microelectronic technique at microelectronic.
Why the ALD technology receives the industry favor, relevant with technical characterstic with its peculiar growing principle.Though the ALD deposit is a kind of chemical vapor deposition (CVD) technology; But with traditional CVD compared with techniques; Still the surperficial saturated chemistry that has big difference very, ALD technology to be based on to carry out in order is from the growth course of restriction, and it is passed in the reaction chamber reacting gas ALT pulse formula.An ALD reaction cycle comprises 4 steps: (1) first kind of reacting precursor gets into reaction chamber and chemisorbed at substrate surface with the mode of pulse; (2) treat that surface adsorption is saturated after, with inert gas unnecessary reacting precursor purge is gone out reaction chamber; (3) then second kind of reacting precursor gets into reaction chamber with the mode of pulse, and reacts with last chemisorbed precursor from the teeth outwards; (4) question response goes out reaction chamber with inert gas with unnecessary reacting precursor and accessory substance purge thereof after fully again.Whole ALD growth course is realized by the repeatedly cycle repeats of one-period.The substantive characteristics of all ALD is exactly that surface reaction reaches capacity; Feasible growth stops automatically; Therefore the thickness of film directly is proportional to the completed number of times of surface reaction; Both the reaction cycle number can just can be realized the accurate control to film thickness through the reaction cycle number of control deposit like this.In addition because it from the surface reaction characteristic of restriction, can form uniform covering to the very big surface of depth-width ratio.Also can control the content of different material in the film through controlling the number of times ratio of homology pulse cycle not in addition.
Summary of the invention
The purpose of this invention is to provide a kind of Ge base mos capacitance that can improve Ge base mos capacitance electric property and preparation method thereof.
The Ge base mos capacitance that the present invention proposes, the GeO that forms by Ge base substrate (101), rapid thermal oxidation
2(103), HfO
2Gate dielectric layer (104) and electrode (105) constitute.
Ge base mos capacitance preparation method of the present invention may further comprise the steps:
1) Ge base substrate is cleaned;
2) cleaned substrate is carried out rapid thermal oxidation (RTO), form GeO
2
The substrate that 3) will pass through rapid thermal oxidation is put into ald chamber, and reaction chamber temperature is 150-300
oC feeds Hf [N (C in order
2H
5) (CH
3)]
4Circulate to accomplish an ALD with deionized water, generate HfO
2Gate dielectric layer; The ALD cycle-index is by HfO
2The thickness requirement of gate dielectric layer is confirmed;
4) at HfO
2Make electrode on the gate dielectric layer.
Above-mentioned steps 1) cleaning process is: earlier Ge base substrate is soaked 5-10 min in ethanol; And then in acetone ultrasonic cleaning 5-10 min; And then with ethanol ultrasonic cleaning 5-10 min in order to removing impurity such as surface and oil contaminant, circulate ultrasonic several times concussion and rinsing to remove surperficial natural GeO with the hydrofluoric acid of 1:50 volume and deionized water in the back several times with deionized water rinsing
x, per step 15-20 s dries up for use with high purity nitrogen at last.
Above-mentioned steps 2) the rapid thermal oxidation process is: the Ge base substrate that will clean puts into 400
oOxidation 3-10 min in the ALD reaction chamber of C, O
2Flow is 400-800 sccm, and GeO directly grows in the reaction cavity of ALD growth high K medium film
2Interface Control layer, this method can avoid its surface to contact back generation chemical reaction with air, thereby can improve interfacial characteristics.
Above-mentioned steps 3) step of a circulation of ALD deposition process is: at first feed Hf [N (C
2H
5) (CH
3)]
4Burst length 1-5 s feeds N then
2Burst length 1-5 s feeds H once more
2O burst length 0.3-1.0 s feeds N at last
2Burst length 0.5-2.0 s.
The present invention adopts the rapid thermal oxidation processing method to form the high-quality GeO of one deck at Ge base substrate surface
2, can prevent the diffusion of Ge, reduce defective electric charge and interface state density, improve interfacial characteristics; The HfO of institute's deposit
2Dielectric layer, thickness can be accurately controlled, the conformal excellent performance, the Interface Control ability is strong, good uniformity.The present invention can improve the electrology characteristic of Ge base mos capacitance greatly, thereby improves the performance of Ge base MOS transistor.
Description of drawings
Fig. 1 is the making flow chart of whole Ge base mos capacitance.
Fig. 2 is the Ge substrat structure before cleaning.
Fig. 3 is the Ge substrat structure after cleaning.
Fig. 4 is the structure behind process rapid thermal oxidation on the Ge substrate.
Fig. 5 is deposit HfO on the substrate after rapid thermal oxidation is handled
2Structure behind the gate medium.
Fig. 6 is the structure behind depositing metal electrode on the gate medium.
Embodiment
The present invention is further detailed explanation with the specific embodiment below in conjunction with the making flow chart of whole Ge base mos capacitance 1, and in the drawings, explanation is for ease amplified or dwindled layer and regional thickness, shown in size do not represent actual size.Although the actual size that reflects device that these figure can not entirely accurate, their zones that still has been complete reflection and form the correlation between the structure.
Step 1: choose commercial monocrystalline Ge sheet, n type Sb mixes, and crystal orientation (100), resistivity 0.21-0.26 Ω cm is as substrate, i.e. 101 layers among Fig. 2, but have the GeO of one deck autoxidation without the Ge substrate surface that cleans
x, i.e. 102 layers among Fig. 2;
Step 2: substrate is put into ethanol soak 10 min;
Step 3: substrate is put into acetone ultrasonic cleaning 10 min;
Step 4: substrate is put into ethanol ultrasonic cleaning 10 min;
Step 5: several times with deionized water rinsing;
Step 6: ultrasonic concussion 15 s of hydrofluoric acid solution that substrate put into 1:50;
Step 7: substrate is taken out with rinsed with deionized water 15 s;
Step 8: repeating step 6 and 7 is several times to remove nature GeO
xLayer;
Step 9: use N
2Substrate is dried up, promptly get Ge base substrate shown in Figure 3;
Step 10: substrate is put into the ALD reaction chamber, feed O
2, rapid thermal oxidation 5min, temperature 400
oC, oxygen flow 600 sccm generate structure as shown in Figure 4,103 layers of high-quality GeO for rapid thermal oxidation formation
2
Step 11: forming high-quality GeO
2After, the ALD reaction cavity begins cooling, drops to the reaction temperature (250 of growth high-k gate dielectric up to its temperature
oC), immediately begin ALD growth HfO
2Dielectric layer feeds Hf source and deionized water in order, meets the requirements of the gate dielectric membrane of period to obtain to require, and when wherein growing, reaction chamber pressure is 2-5 torr, and the time of a cycle period feeding gas is respectively Hf [N (C
2H
5) (CH
3)]
4: N
2: H
2O:N
2=1.0 s:3.0 s:0.3 s:1.0 s form structure as shown in Figure 5, and 104 layers is the HfO of ALD deposit
2
Step 12: take out the Ge sheet in the reaction chamber, deposition of electrode.Multiple materials such as electrode material can aluminium, gold, platinum, titanium nitride, manufacture method can adopt kinds of processes such as evaporation, sputter, forms structure shown in Figure 6, the electrode that 105 representatives form.
Claims (5)
1. germanium base mos capacitance is characterized in that the GeO that forms by Ge base substrate, at Ge base substrate rapid thermal oxidation
2, at GeO
2Go up HfO by the atomic layer deposition growth
2Gate dielectric layer and electrode constitute.
2. the preparation method of a germanium base mos capacitance is characterized in that concrete steps are:
1) Ge base substrate is cleaned;
2) cleaned substrate is carried out rapid thermal oxidation, form GeO
2
The substrate that 3) will pass through rapid thermal oxidation is put into the ALD reaction chamber, and reaction chamber temperature is 150-300
oC, the operating pressure of reaction chamber remains on 2-5 torr; Feed Hf [N (C in order
2H
5) (CH
3)]
4Circulate to accomplish an ALD with deionized water, generate HfO
2Gate dielectric layer; The ALD cycle-index is by HfO
2The thickness requirement of gate dielectric layer is confirmed;
4) at HfO
2Make electrode on the gate dielectric layer.
3. preparation method according to claim 1 is characterized in that the step 1) cleaning process is: earlier Ge base substrate is soaked 5-10 min in ethanol, again ultrasonic cleaning 5-10 min in acetone; Then with ethanol ultrasonic cleaning 5-10 min in order to remove surface and oil contaminant impurity, use deionized water rinsing, with the hydrofluoric acid of 1:50 volume and the deionized water circulating ultrasonic shakes and rinsing to remove surperficial natural GeO
x, per step 15-20 s dries up for use with high purity nitrogen at last.
4. preparation method according to claim 2 is characterized in that step 2) the rapid thermal oxidation process is: the Ge base substrate that will clean puts into 400
oOxidation 3-10 min in the ALD reaction chamber of C, O
2Flow is 400-800 sccm.
5. the step of preparation method according to claim 2, its a characteristic ALD circulation in step 3) is: at first feed Hf [N (C
2H
5) (CH
3)]
4Burst length 1-5 s feeds N then
2Burst length 1-5 s; Feed H then
2O burst length 0.3-1.0 s feeds N at last
2Burst length 0.5-2.0 s.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103219381A (en) * | 2013-01-16 | 2013-07-24 | 南京大学 | Germanium (Ge) base tri-gate device and manufacturing method thereof |
| CN103413837A (en) * | 2013-07-08 | 2013-11-27 | 复旦大学 | MOS capacitor of germanium based high dielectric constant insulated medium and preparation method thereof |
| CN106601587A (en) * | 2016-11-29 | 2017-04-26 | 东莞市广信知识产权服务有限公司 | Ge base MOS device structure |
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| US20060019466A1 (en) * | 2004-07-22 | 2006-01-26 | Nayfeh Ammar M | Germanium substrate-type materials and approach therefor |
| CN1956147A (en) * | 2005-10-26 | 2007-05-02 | 国际商业机器公司 | Ge-based semiconductor structure and manufacturing method thereof |
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| US20080029790A1 (en) * | 2006-08-03 | 2008-02-07 | Micron Technology, Inc. | ALD of silicon films on germanium |
| CN101800167A (en) * | 2009-02-09 | 2010-08-11 | 中国科学院微电子研究所 | Method for preparing metal-oxide-semiconductor capacitor on germanium substrate |
-
2011
- 2011-11-08 CN CN2011103489001A patent/CN102509734A/en active Pending
Patent Citations (5)
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| US20060019466A1 (en) * | 2004-07-22 | 2006-01-26 | Nayfeh Ammar M | Germanium substrate-type materials and approach therefor |
| CN1985352A (en) * | 2004-07-30 | 2007-06-20 | 飞思卡尔半导体公司 | Interfacial layer for use with high k dielectric materials |
| CN1956147A (en) * | 2005-10-26 | 2007-05-02 | 国际商业机器公司 | Ge-based semiconductor structure and manufacturing method thereof |
| US20080029790A1 (en) * | 2006-08-03 | 2008-02-07 | Micron Technology, Inc. | ALD of silicon films on germanium |
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| Title |
|---|
| ANNELIES DELABIE: "《Effective electrical passivation of Ge（100）for high-k gate dielectric layers using germanium oxide》", 《APPLIED PHYSICS LETTERS》, vol. 91, no. 082904, 22 August 2007 (2007-08-22) * |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103219381A (en) * | 2013-01-16 | 2013-07-24 | 南京大学 | Germanium (Ge) base tri-gate device and manufacturing method thereof |
| CN103219381B (en) * | 2013-01-16 | 2016-03-30 | 南京大学 | Ge base tri-gate devices and manufacture method |
| CN103413837A (en) * | 2013-07-08 | 2013-11-27 | 复旦大学 | MOS capacitor of germanium based high dielectric constant insulated medium and preparation method thereof |
| CN106601587A (en) * | 2016-11-29 | 2017-04-26 | 东莞市广信知识产权服务有限公司 | Ge base MOS device structure |
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Application publication date: 20120620 |