CN102737999B - Method for preparing metal-oxide-semiconductor field effect transistor on germanium substrate - Google Patents

Method for preparing metal-oxide-semiconductor field effect transistor on germanium substrate Download PDF

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CN102737999B
CN102737999B CN201110090483.5A CN201110090483A CN102737999B CN 102737999 B CN102737999 B CN 102737999B CN 201110090483 A CN201110090483 A CN 201110090483A CN 102737999 B CN102737999 B CN 102737999B
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nitrogen
hafnium
metal
nitride film
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CN102737999A (en
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胡爱斌
许高博
徐秋霞
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Ruili Flat Core Microelectronics Guangzhou Co Ltd
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Institute of Microelectronics of CAS
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Abstract

The invention provides a method for preparing a metal-oxide-semiconductor field effect transistor on a germanium substrate. The method comprises: cleaning a germanium sheet; successively depositing a silicon nitride film and a hafnium nitride film on a cleaned germanium substrate in an atmosphere of argon and nitrogen by adopting a method of radio frequency magnetron reaction sputtering, and the deposition of multiple layers of the silicon nitride and the hafnium nitride stacking-layer is carried out for multiple times; rapidly thermal annealing is carried out to form a hafnium silicon oxygen nitrogen medium in an atmosphere of the nitrogen; depositing a metal electrode material by adopting the radio frequency magnetron reaction sputtering method is carried out, such that a gate electrode figure is formed; performing source-drain ion implantation and activating the annealing to form a heavy-doped source-drain area; depositing a metal and forming an ohmic contact of a source-drain end; and lastly, annealing and metallization are carried out in a furnace tube in an atmosphere of the nitrogen. According to the invention, a silicon element is doped into a hafnium-based high dielectric constant medium, thereby avoiding a problem of producing oxides containing a large amount of defective germanium in annealing process after deposition of gate dielectric and annealing process after the formation of the metal electrode and reducing fixed charges at interface and charge trapping.

Description

Metal-oxide semiconductor fieldeffect transistor method prepared by germanium substrate
Technical field
The invention belongs to nanometer feature sizes technical field of semiconductor device preparation, particularly relate to and adopt hafnium base high-dielectric-coefficient grid medium to prepare the method for Metal-oxide-semicondutor (MOS) field-effect transistor on germanium substrate.
Background technology
In history, first transistor and first piece of integrated circuit all adopt germanium backing material to prepare.Due to thermodynamic phase and the characteristic soluble in water of the oxide of germanium, it is made to be not suitable as gate dielectric material; Silicon dioxide then has excellent physical characteristic and electrology characteristic, therefore adopt the metal-oxide semiconductor fieldeffect transistor of silicon substrate (MOSFET) in the past four obtain investigation and application widely during the decade.Over 40 years, integrated circuit technique is by Moore's Law sustainable development, and characteristic size constantly reduces, and integrated level improves constantly.Along with the continuous reduction of device size, gate oxide thickness is also thereupon thinning.At present, the characteristic size of MOSFET enters sub-50 nm, and gate oxide (silicon dioxide or nitride-monox) thickness is also reduced to below 1.2 nanometers.If still adopt traditional silicon dioxide gate medium, gate medium Direct Tunneling increases anxious for exponentially rule.In order to head it off, adopt hafnium base high dielectric constant to obtain as novel grid medium and study widely.In identical equivalent oxide thickness situation, high dielectric constant has thicker physical thickness, and therefore gate medium Direct Tunneling reduces greatly, and power consumption significantly reduces.
The appearance of the hafnium base high dielectric constant MOSFET of germanium substrate the is regained attention of people.Compare with silicon, germanium has larger electronics and hole mobility, and the MOSFET therefore prepared has higher speed.Germanium is different with hafnium base high dielectric constant interfacial characteristics from silicon with hafnium base high dielectric constant interfacial characteristics.In heat treatment process after high dielectric constant deposit, oxygen atom is easy to be diffused into germanium and high dielectric constant interface and germanium atom and reacts and generate the oxide of germanium.Different from silicon dioxide, the oxide of germanium contains a large amount of defect states, can produce a large amount of fixed charge at interfaces or interfacial state in interface.
Therefore, be necessary to find the performance that a kind of method avoids affecting due to the generation of the oxide of germanium device.
In addition, a lot of physicochemical properties of germanium are different with silicon, and such as germanium can not adopt 3# and the 1# cleaning fluid in silicon technology to clean, and the activationary temperature after foreign ion injects is not identical with silicon yet.Therefore for the preparation of germanium MOSFET, need to research and develop brand-new technological process.
Summary of the invention
The object of the present invention is to provide a kind of method preparing metal-oxide semiconductor fieldeffect transistor (MOSFET) on germanium substrate.
For achieving the above object, the method preparing metal-oxide semiconductor fieldeffect transistor on germanium substrate provided by the invention, mainly comprises:
1) clean germanium wafer: soak in acetone and ethanol respectively, be then oxidized in hydrogen peroxide solution, then corrode in hydrochloric acid solution, water dries up with nitrogen after rinsing;
2) germanium wafer after cleaning adopts the method for superconducting RF deposition silicon nitride film and hafnium nitride film successively in the atmosphere of argon gas and nitrogen, repeat deposit multilayer silicon nitride and hafnium nitride lamination;
3) in the atmosphere of nitrogen, rapid thermal annealing forms hafnium silicon oxygen nitrogen medium;
4) on hafnium silicon oxygen nitrogen medium, form the figure of photoresist;
5) the method depositing metal electrode material of superconducting RF is adopted;
6) peel off to form electrode pattern to metal electrode material;
7) source and drain areas ion implantation and in 350 degrees Celsius to 450 degrees Celsius annealing activate;
8) adopt the method depositing metal of superconducting RF and peel off to form source and drain end ohmic contact and metal connecting line to metal;
9) in the atmosphere of nitrogen in boiler tube annealed metal.
In described method, the step that step 1 cleans germanium wafer comprises: soak 5-20 minute in acetone, 5-20 minute is soaked in ethanol, deionized water rinsing, then in hydrogen peroxide solution, be oxidized 10-120 second, deionized water rinsing, in hydrochloric acid solution, then corrode 30-300 second, deionized water rinsing, hydrogen peroxide solution oxidation and hydrochloric acid solution corrosion repeat 2-5 time; Then deionized water rinsing, dries up with nitrogen.
In described method, the concentration of volume percent of hydrogen peroxide solution is 2%-10%, and the concentration of volume percent of hydrochloric acid solution is 5%-20%.
In described method, the step of step 2 deposition silicon nitride film and hafnium nitride film successively comprises: before sputtering, sputtering chamber vacuum is evacuated to 1 × 10 -6holder is to 1 × 10 -7between holder, be filled with nitrogen and argon gas, the volume ratio of the two is between 1: 20 to 6: 20, and then sputter silicon target and hafnium target successively, deposition silicon nitride film and hafnium nitride film, repeat 1 time to 10 times deposit multilayer silicon nitride and hafnium nitride lamination.
In described method, the thickness of silicon nitride film is 2 dust-6 dusts, and the thickness of hafnium nitride film is 2 dust-9 dusts.
In described method, the step of step 3 rapid thermal annealing comprises: rapid thermal annealing 30 seconds to 120 seconds at the temperature of 300 degrees Celsius to 600 degrees Celsius in the atmosphere of nitrogen.
In described method, the step of step 5 depositing metal electrode material comprises: before sputtering, sputtering chamber vacuum is evacuated to 1 × 10 -6holder is to 1 × 10 -7between holder, be filled with nitrogen and argon gas, the volume ratio of the two is between 1: 20 to 6: 20, then sputter tantalum target or titanium target, deposit tantalum nitride electrode film or titanium nitride electrodes film, the thickness of tantalum nitride electrode film and titanium nitride electrodes film is 500 dust-2000 dusts.
In described method, the step 7 ion implantation step that also annealing activates comprises: the ion of injection is BF2, and energy is between 20 kilo electron volts to 60 kilo electron volts, and dosage is between 2E15 to 6E15; Anneal 5 minutes to 60 minutes.
In described method, step 8 depositing metal is also peeled off to be formed in the step of electrode pattern to metal, and described metal is metallic aluminium, Titanium, nitride metal titanium or their laminated construction.
In described method, the step of step 9 annealed metal comprises: in the atmosphere of nitrogen, under 500 degrees Celsius, anneals 20 minutes to 60 minutes in boiler tube for 300 degrees Celsius.
Compared with known technology, the present invention has following beneficial effect:
1, the chemical reagent that the present invention adopts is the reagent that silica-based MOSFET technique is commonly used; Adopt hafnium silicon oxygen nitrogen high dielectric constant and metal gate electrode material, with silica-based MOSFET standard technology, there is favorable compatibility.
2, the present invention adopts the method for mixing element silicon in hafnium base high dielectric constant, effectively can stop the diffusion of oxygen atom, the germanium atom avoiding oxygen atom and interface in heat treatment process subsequently reacts and generates the oxide of germanium, thus decreases the generation of boundary defect state.
3, the temperature of source and drain impurity activation of the present invention is lower, and what be beneficial to hafnium base high dielectric constant and metal gate electrode is integrated.The method technique is simple, and the difficulty of preparation and cost low, there is very high application.
Accompanying drawing explanation
Fig. 1 is the method flow diagram preparing MOSFET on germanium substrate provided by the invention;
Fig. 2 is the relation curve adopting longitudinal effective electric field in hafnium silicon oxygen nitrogen medium and the germanium MOSFET of tantalum nitride electrode and the hole mobility of silicon MOSFET and raceway groove.
Embodiment
The present invention mainly comprises:
(1) a kind of cleaning method of germanium substrate is provided;
(2) provide the preparation method of gate medium on a kind of germanium substrate, with solve the annealing after gate dielectric deposition and metal electrode formed after annealing process in generate the problem of the oxide of the germanium containing a large amount of defect state;
(3) a kind of method forming heavy-doped source drain region on germanium substrate is provided.
For making the object, technical solutions and advantages of the present invention clearly understand, below in conjunction with specific embodiment, and with reference to accompanying drawing, the present invention is described in more detail.
The present invention adopts hafnium silicon oxygen nitrogen high dielectric constant as gate medium to improve the interfacial characteristics of the MOSFET on germanium substrate.As shown in Figure 1, Fig. 1 is the method flow diagram preparing MOSFET on germanium substrate provided by the invention, and the method comprises:
Step 101: cleaning germanium wafer;
Step 102: germanium wafer after cleaning adopts the method for superconducting RF deposition silicon nitride film and hafnium nitride film successively in the atmosphere of argon gas and nitrogen, then repeat once;
Step 103: rapid thermal annealing forms hafnium silicon oxygen nitrogen medium in the atmosphere of nitrogen;
Step 104: form photoetching offset plate figure on hafnium silicon oxygen nitrogen medium;
Step 105: the method depositing metal electrode material adopting superconducting RF;
Step 106: peel off to form electrode pattern to metal electrode material;
Step 107: the ion implantation of source and drain areas activation of annealing;
Step 108: adopt the method depositing metal of superconducting RF and peel off to form source and drain end ohmic contact and metal connecting line to metal;
Step 109: in the atmosphere of nitrogen in boiler tube annealed metal.
Further describe technical scheme provided by the invention below in conjunction with specific embodiment, the concrete technology step of the present embodiment is as follows:
(1) germanium wafer is cleaned: soak 10 minutes in acetone, soak 5 minutes in ethanol, deionized water rinsing, then in hydrogen peroxide solution, 60 seconds are oxidized, deionized water rinsing, then corrode 30 seconds in hydrochloric acid solution, deionized water rinsing, hydrogen peroxide solution oxidation and hydrochloric acid solution corrode repetition 3 times; Then deionized water rinsing, dries up with nitrogen.Wherein, the concentration of described hydrogen peroxide solution is 5%, and the concentration of described hydrochloric acid solution is 10%.
(2) germanium wafer after cleaning adopts the method for superconducting RF deposition silicon nitride film and hafnium nitride film successively in the atmosphere of argon gas and nitrogen: before sputtering, sputtering chamber vacuum is evacuated to 8 × 10 -7holder, be filled with nitrogen and argon gas, nitrogen and the volume ratio both argon gas are 5: 20, and then sputter silicon target and hafnium target successively, deposition silicon nitride film and hafnium nitride film, wherein within a cycle, the thickness of silicon nitride film is 6 dusts, and the thickness of hafnium nitride film is 9 dusts.
(3) rapid thermal annealing: rapid thermal annealing 60 seconds under 500 degree celsius temperature in the atmosphere of nitrogen.
(4) form photoetching offset plate figure: adopt AZ5214 photoresist, gluing, exposure, development, form the figure of photoresist.
(5) the method depositing metal electrode material of superconducting RF is adopted: before sputtering, sputtering chamber vacuum is evacuated to 8 × 10 -7holder, be filled with nitrogen and argon gas, the volume ratio of the two is 4: 20, then sputter tantalum target, deposit tantalum nitride electrode film, and thickness is 1000 dusts.
(6) peel off to form electrode pattern to metal electrode material: soak 10 hours in acetone soln, remove photoresist and metallic film thereon.
(7) ion implantation of source and drain areas and impurity activation anneal, the ion of injection is BF2, and energy is 40 kilo electron volts, dosage 4E15; Then 400 degrees Celsius of annealing 40 minutes.
(8) adopt method deposit one deck 500 dust nitride metal titanium and the 1500 dust metallic aluminiums of superconducting RF, then peel off and form figure.
(9) in the atmosphere of nitrogen in boiler tube 300 degrees Celsius annealing 40 minutes.
Fig. 2 is the relation curve adopting longitudinal effective electric field in hafnium silicon oxygen nitrogen medium and the germanium MOSFET of tantalum nitride electrode and the hole mobility of silicon MOSFET and raceway groove.When the longitudinal effective electric field in raceway groove is 0.1 megavolt every centimetre, the hole mobility of germanium MOSFET and silicon MOSFET is respectively 120 centimeters per volt seconds and 46 centimeters per volt seconds, and the hole mobility of germanium MOSFET is 2.6 times of silicon; When the longitudinal effective electric field in raceway groove is 0.4 megavolt every centimetre, the hole mobility of germanium MOSFET and silicon MOSFET is respectively 54 centimeters per volt seconds and 27 centimeters per volt seconds, and the hole mobility of germanium MOSFET is 2 times of silicon.Above result shows to adopt the germanium MOSFET of hafnium silicon oxygen nitrogen medium and tantalum nitride electrode to have larger hole mobility, and then has higher operating rate.
Above-described specific embodiment; object of the present invention, technical scheme and beneficial effect are further described; be understood that; the foregoing is only specific embodiments of the invention; be not limited to the present invention; within the spirit and principles in the present invention all, any amendment made, equivalent replacement, improvement etc., all should be included within protection scope of the present invention.

Claims (8)

1. on germanium substrate, prepare a method for metal-oxide semiconductor fieldeffect transistor, mainly comprise:
1) clean germanium wafer, soak respectively, be then oxidized in hydrogen peroxide solution, then corrode in hydrochloric acid solution in acetone and ethanol, water dries up with nitrogen after rinsing;
2) germanium wafer after cleaning adopts the method for superconducting RF deposition silicon nitride film and hafnium nitride film successively in the atmosphere of argon gas and nitrogen, repeat deposit multilayer silicon nitride and hafnium nitride lamination; The thickness of silicon nitride film is 2 dust-6 dusts, and the thickness of hafnium nitride film is 2 dust-9 dusts;
3) in the atmosphere of nitrogen, rapid thermal annealing forms hafnium silicon oxygen nitrogen medium;
4) on hafnium silicon oxygen nitrogen medium, form the figure of photoresist;
5) the method depositing metal electrode material of superconducting RF is adopted;
6) peel off to form electrode pattern to metal electrode material;
7) source and drain areas ion implantation and 350 degrees Celsius to 450 degrees Celsius annealing activate;
8) adopt the method depositing metal of superconducting RF and peel off to form source and drain end ohmic contact and metal connecting line to metal;
9) in the atmosphere of nitrogen in boiler tube annealed metal.
2. method according to claim 1, wherein, the step that step 1 cleans germanium wafer comprises: soak 5-20 minute in acetone, soak 5-20 minute in ethanol, deionized water rinsing, in hydrogen peroxide solution, be then oxidized 10-120 second, deionized water rinsing, then in hydrochloric acid solution, corrode 30-300 second, deionized water rinsing, hydrogen peroxide solution oxidation and hydrochloric acid solution corrosion repeat 2-5 time; Then deionized water rinsing, dries up with nitrogen.
3. method according to claim 1 and 2, wherein, the concentration of volume percent of hydrogen peroxide solution is 2%-10%, and the concentration of volume percent of hydrochloric acid solution is 5%-20%.
4. method according to claim 1, wherein, the step of step 2 deposition silicon nitride film and hafnium nitride film successively comprises: before sputtering, sputtering chamber vacuum is evacuated to 1 × 10 -6holder is to 1 × 10 -7between holder, be filled with nitrogen and argon gas, the volume ratio of the two is between 1:20 to 6:20, and then sputter silicon target and hafnium target successively, deposition silicon nitride film and hafnium nitride film, repeat 1 time to 10 times deposit multilayer silicon nitride and hafnium nitride lamination.
5. method according to claim 1, wherein, the step of step 3 rapid thermal annealing comprises: rapid thermal annealing 30 seconds to 120 seconds at the temperature of 300 degrees Celsius to 600 degrees Celsius in the atmosphere of nitrogen.
6. method according to claim 1, wherein, the step of step 5 depositing metal electrode material comprises: before sputtering, sputtering chamber vacuum is evacuated to 1 × 10 -6holder is to 1 × 10 -7between holder, be filled with nitrogen and argon gas, the volume ratio of the two is between 1:20 to 6:20, then sputter tantalum target or titanium target, deposit tantalum nitride electrode film or titanium nitride electrodes film, the thickness of tantalum nitride electrode film and titanium nitride electrodes film is 500 dust-2000 dusts.
7. method according to claim 1, wherein, the step 7 ion implantation step that also annealing activates comprises: the ion of injection is BF 2, energy is between 20 kilo electron volts to 60 kilo electron volts, and dosage is between 2E15 to 6E15; Anneal 5 minutes to 60 minutes.
8. method according to claim 1, wherein, the step of step 9 annealed metal comprises: in the atmosphere of nitrogen, under 500 degrees Celsius, anneals 20 minutes to 60 minutes in boiler tube for 300 degrees Celsius.
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CN101447420A (en) * 2007-11-28 2009-06-03 中国科学院微电子研究所 Method for preparing high-dielectric-coefficient grid medium membrane hafnium silicon oxygen nitrogen
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

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Publication number Priority date Publication date Assignee Title
CN101447420A (en) * 2007-11-28 2009-06-03 中国科学院微电子研究所 Method for preparing high-dielectric-coefficient grid medium membrane hafnium silicon oxygen nitrogen
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

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