CN102103983B - Method of preparing metal oxide semiconductor capacitor on germanium substrate - Google Patents
Method of preparing metal oxide semiconductor capacitor on germanium substrate Download PDFInfo
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- CN102103983B CN102103983B CN2009102427674A CN200910242767A CN102103983B CN 102103983 B CN102103983 B CN 102103983B CN 2009102427674 A CN2009102427674 A CN 2009102427674A CN 200910242767 A CN200910242767 A CN 200910242767A CN 102103983 B CN102103983 B CN 102103983B
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Abstract
The invention discloses a method of preparing a metal oxide semiconductor (MOS) capacitor on a germanium substrate by employing a hafnium silicon oxygen nitrogen medium, comprising the steps of: cleaning a germanium wafer; successively performing deposition of a silicon nitride film and a hafnium nitride film on the cleaned germanium wafer, and repeating deposition many times to form a multilayer silicon nitride and hafnium nitride laminate; performing rapid thermal annealing in a nitrogen atmosphere; forming a photoresist figure through gluing, exposure and development; performing deposition of a metal electrode material; peeling the metal electrode material to form an electrode figure; sputtering a layer of metal aluminum on the back side of the germanium substrate; and performing annealing and metallization in a furnace tube in the nitrogen atmosphere. According to the method of the invention, silicon elements are doped into a hafnium-based high-dielectric constant medium, which can avoid the problem that the oxide containing a large amount of defect state germanium is generated in the annealing processes after gate medium deposition and metal electrode formation, reduce the immobilized charges and charge capture centers at an interface, and obtain a germanium MOS capacitor with high electrical performance.
Description
Technical field
The present invention relates to nanometer feature sizes semiconductor device preparing technical field, relate in particular to and on the germanium substrate, adopt hafnium base high-dielectric-coefficient grid medium to prepare the method for Metal-oxide-semicondutor (MOS) electric capacity.
Background technology
In history, first transistor and first integrated circuit all adopt the preparation of germanium backing material.Because the thermodynamic phase of the oxide of germanium and characteristic soluble in water are not suitable for as gate dielectric material it; Silicon dioxide then has excellent physical characteristics and electrology characteristic, the metal-oxide semiconductor transistor (MOSFET) that therefore adopts silicon substrate in the past four obtained extensive studies and application during the decade.Over 40 years, integrated circuit technique is by the sustainable development of mole law, and characteristic size is constantly dwindled, and integrated level improves constantly.Along with constantly reducing of device size, gate oxide thickness is attenuate thereupon also.At present, the characteristic size of MOSFET has got into inferior 50 nanometers, and gate oxide (silicon dioxide or nitride-monox) thickness also is reduced to below 1.2 nanometers.If still adopt the traditional silicon dioxide gate medium, gate medium direct Tunneling electric current suddenly increases the exponentially rule.For head it off, adopt hafnium base high dielectric constant to obtain extensive studies as novel gate medium.Under identical equivalent oxide thickness situation, high dielectric constant has thicker physical thickness, so gate medium direct Tunneling electric current reduces greatly, and power consumption significantly reduces.
The appearance of hafnium base high dielectric constant makes the MOSFET of germanium substrate regain people's attention.Compare with silicon, germanium has bigger electronics and hole mobility, and therefore the MOSFET of preparation has higher speed.Germanium is different with hafnium base high dielectric constant interfacial characteristics with silicon with hafnium base high dielectric constant interfacial characteristics.In the heat treatment process after the high dielectric constant deposit, oxygen atom is easy to be diffused into germanium and high dielectric constant and reacts with germanium atom at the interface and generate the oxide of germanium.Different with silicon dioxide, the oxide of germanium contains a large amount of defect states, can produce a large amount of interface fixed charge or interfacial state at the interface.
Therefore, be necessary to seek the performance that a kind of method avoids influencing owing to the generation of the oxide of germanium device.
Summary of the invention
The technical problem that (one) will solve
In view of this; Main purpose of the present invention is to provide a kind of method that on the germanium substrate, prepares mos capacitance; Problem with the oxide that solves the germanium that generation in the annealing process after annealing after the gate medium deposit forms with metal electrode contains a large amount of defect states; Reduce at the interface fixed charge and electric charge capture center, obtain the good mos capacitance of electric property.
(2) technical scheme
For achieving the above object, the invention provides a kind of method that on the germanium substrate, prepares Metal-oxide-semicondutor electric capacity, this method comprises:
Step 1: clean germanium wafer;
Step 2:, and repeat 1 to 10 deposit multilayer silicon nitride and hafnium nitride lamination at the method that adopts the radio frequency magnetron reactive sputtering on the germanium wafer after the cleaning deposition silicon nitride film and hafnium nitride film successively in the atmosphere of argon gas and nitrogen;
Step 3: rapid thermal annealing forms the hafnium silicon oxygen nitrogen medium in the atmosphere of nitrogen;
Step 4: the figure that on the germanium wafer after the annealing, forms photoresist;
Step 5: the method depositing metal electrode material that adopts the radio frequency magnetron reactive sputtering;
Step 6: metal electrode material is peeled off to form electrode pattern;
Step 7: at the back spatter layer of metal aluminium of germanium substrate to reduce the contact resistance at the back side;
Step 8: in the atmosphere of nitrogen in boiler tube annealed metalization.
In the such scheme, the step of cleaning germanium wafer described in the step 1 comprises: in acetone, soaked 5～20 minutes, soaked in the ethanol 5～20 minutes; Deionized water rinsing; Oxidation 10～120 seconds in hydrogen peroxide solution then, deionized water rinsing then corroded in hydrochloric acid solution 30～300 seconds; Deionized water rinsing, hydrogen peroxide solution oxidation and hydrochloric acid solution corrosion repetition 2 to 5 times; Deionized water rinsing dries up with nitrogen then.
In the such scheme, in said hydrogen peroxide solution and the hydrochloric acid solution, the concentration of hydrogen peroxide solution (percent by volume) is 2% to 10%, and the concentration of hydrochloric acid solution (percent by volume) is 5% to 20%.
In the such scheme; At the method that adopts the radio frequency magnetron reactive sputtering on the germanium wafer after the cleaning deposition silicon nitride film and hafnium nitride film successively in the atmosphere of argon gas and nitrogen, the step that repeats repeatedly deposit multilayer silicon nitride and hafnium nitride lamination comprises: before sputter, the sputtering chamber vacuum is evacuated to 1 * 10 described in the step 2
-6Hold in the palm 1 * 10
-7Between the holder, charge into nitrogen and argon gas, the volume ratio of the two is between 1: 20 to 6: 20, sputter silicon target and hafnium target successively then, and deposition silicon nitride film and hafnium nitride film repeat 1 to 10 deposit multilayer silicon nitride and hafnium nitride lamination.
In the such scheme, in described silicon nitride film and the hafnium nitride film thickness of silicon nitride film be 2 dusts to 6 dusts, the thickness of hafnium nitride film is that 2 dusts are to 9 dusts.
In the such scheme, described in the step 3 in the atmosphere of nitrogen the step of rapid thermal annealing comprise: rapid thermal annealing 30 seconds to 120 seconds under 300 degrees centigrade to 600 degrees centigrade the temperature in the atmosphere of nitrogen.
In the such scheme, adopt the step of the method depositing metal electrode material of radio frequency magnetron reactive sputtering to comprise described in the step 5: before sputter, the sputtering chamber vacuum to be evacuated to 1 * 10
-6Hold in the palm 1 * 10
-7Between the holder, charge into nitrogen and argon gas, the volume ratio of the two is between 1: 20 to 6: 20, sputter tantalum target or titanium target then, and deposit tantalum nitride electrode film or titanium nitride electrode film, its thickness are that 500 dusts are to 2000 dusts.
In the such scheme, the back spatter layer of metal aluminium at the germanium substrate described in the step 7 comprises with the step that reduces back side contact resistance: at the back spatter layer of metal aluminium of germanium substrate, thickness is that 2000 dusts are to 10000 dusts.
In the such scheme, described in the step 8 in the atmosphere of nitrogen in boiler tube the step of annealed metalization comprise: in the atmosphere of nitrogen, under 300 degrees centigrade to 500 degrees centigrade condition, in boiler tube annealing 20 minutes to 60 minutes.
(3) beneficial effect
Can find out that from technique scheme the present invention has following beneficial effect:
1, this method that on the germanium substrate, prepares mos capacitance provided by the invention adopts hafnium silicon oxygen nitrogen high dielectric constant and metal gate electrode material, has favorable compatibility with silica-based standard technology.
2, this method that on the germanium substrate, prepares mos capacitance provided by the invention; Be employed in the method for mixing element silicon in the hafnium base high dielectric constant; Can effectively stop the diffusion of oxygen atom; Avoid in heat treatment process subsequently oxygen atom and germanium atom at the interface to react and generated the oxide of germanium, thereby reduced the generation of boundary defect attitude.
3, this method that on the germanium substrate, prepares mos capacitance provided by the invention can be applied in the preparation of MOSFET on the germanium substrate.This method technology is simple, and the difficulty and the cost of preparation are low, have very high application.
Description of drawings
Fig. 1 is the method flow diagram that on the germanium substrate, prepares mos capacitance provided by the invention;
Fig. 2 is the capacitance-voltage curve that adopts hafnium oxynitride (HfON) medium and the tantalum nitride electrode-gate medium-germanium electric capacity that adopts hafnium silicon oxygen nitrogen (HfSiON) medium;
Fig. 3 is the current-voltage curve that adopts hafnium oxynitride (HfON) medium and the tantalum nitride electrode-gate medium-germanium electric capacity that adopts hafnium silicon oxygen nitrogen (HfSiON) medium.
Embodiment
For making the object of the invention, technical scheme and advantage clearer, below in conjunction with specific embodiment, and with reference to accompanying drawing, to further explain of the present invention.
The present invention adopts the hafnium silicon oxygen nitrogen high dielectric constant to improve the interfacial characteristics of the mos capacitance on the germanium substrate as gate medium.As shown in Figure 1, Fig. 1 is the method flow diagram that on the germanium substrate, prepares mos capacitance provided by the invention, and this method comprises:
Step 101: clean germanium wafer;
Step 102:, repeat then once at the method that adopts the radio frequency magnetron reactive sputtering on the germanium wafer after the cleaning deposition silicon nitride film and hafnium nitride film successively in the atmosphere of argon gas and nitrogen;
Step 103: rapid thermal annealing forms the hafnium silicon oxygen nitrogen medium in the atmosphere of nitrogen;
Step 104: on the germanium wafer after the annealing, form the photoresist figure;
Step 105: the method depositing metal electrode material that adopts the radio frequency magnetron reactive sputtering;
Step 106: metal electrode material is peeled off to form electrode pattern;
Step 107: at the back spatter layer of metal aluminium of germanium substrate to reduce the contact resistance at the back side;
Step 108: in the atmosphere of nitrogen in boiler tube annealed metalization.
Below in conjunction with specific embodiment further explain technical scheme provided by the invention, the concrete processing step of present embodiment is following:
(1) cleans germanium wafer: in acetone, soaked 10 minutes, soaked 5 minutes deionized water rinsing in the ethanol; Oxidation 60 seconds in hydrogen peroxide solution then, deionized water rinsing, then corrosion 30 seconds in hydrochloric acid solution; Deionized water rinsing, hydrogen peroxide solution oxidation and hydrochloric acid solution corrosion repetition 3 times; Deionized water rinsing dries up with nitrogen then.Wherein, the concentration of said hydrogen peroxide solution is 5%, and the concentration of said hydrochloric acid solution is 10%.
(2) at the method that adopts the radio frequency magnetron reactive sputtering on the germanium wafer after the cleaning deposition silicon nitride film and hafnium nitride film successively in the atmosphere of argon gas and nitrogen: before sputter, the sputtering chamber vacuum is evacuated to 8 * 10
-7Holder charges into nitrogen and argon gas, sputter silicon target and hafnium target successively then, and deposition silicon nitride film and hafnium nitride film,, the two ratio of nitrogen and argon gas is 5: 20, and wherein the thickness of silicon nitride film is 6 dusts in one-period, and the thickness of hafnium nitride film is 9 dusts.
(3) rapid thermal annealing in the atmosphere of nitrogen: rapid thermal annealing 60 seconds under 500 degree celsius temperature in the atmosphere of nitrogen.
(4) form the photoresist figure: adopt the AZ5214 photoresist, gluing, exposure is developed, and forms the figure of photoresist.
(5) the method depositing metal electrode material of employing radio frequency magnetron reactive sputtering: before sputter, the sputtering chamber vacuum is evacuated to 8 * 10
-7Holder charges into nitrogen and argon gas, and the ratio of the two is 4: 20, sputter tantalum target then, and deposit tantalum nitride electrode film, thickness are 1000 dusts.
(6) metal electrode material is peeled off to form electrode pattern: in acetone soln, soaked 10 hours, remove photoresist and metallic film above that.
(7) at the back spatter layer of metal aluminium of germanium substrate to reduce the contact resistance at the back side: at the back spatter layer of metal aluminium of germanium substrate, thickness is 8000 dusts.
(8) in the atmosphere of nitrogen, in boiler tube, anneal: in the atmosphere of nitrogen, under 400 degrees centigrade condition, annealing is 40 minutes in boiler tube.
Fig. 2 shows the capacitance-voltage curve that adopts hafnium oxynitride medium and the tantalum nitride gate electrode-gate medium-germanium electric capacity that adopts the hafnium silicon oxygen nitrogen medium.Annealing temperature after metal gate electrode forms is 300 degrees centigrade or 400 degrees centigrade, and the time is 40 minutes.For the situation that adopts the hafnium oxynitride medium; Adopt the radio frequency magnetron reactive sputtering the method deposit hafnium nitride of 75 dusts; For the situation that adopts the hafnium silicon oxygen nitrogen medium, adopt the radio frequency magnetron reactive sputtering the method deposit gross thickness be the silicon nitride of 12 dusts and the hafnium nitride of 18 dusts.Under four kinds of situation: (a) hafnium oxynitride medium, 300 degrees centigrade of 40 minutes metal gate electrodes form after annealing; (b) hafnium oxynitride medium, 400 degrees centigrade of 40 minutes metal gate electrodes form after annealing; (c) hafnium silicon oxygen nitrogen medium, 300 degrees centigrade of 40 minutes metal gate electrodes form after annealing; (d) hafnium silicon oxygen nitrogen medium, 400 degrees centigrade of 40 minutes metal gate electrodes form after annealing, and flat band voltage is respectively-0.73V ,-1.0V ,-0.35V and 0.03V.The work function of tantalum nitride and germanium is respectively 4.5V and 4.29V, and then the flat band voltage under the ideal situation is 0.21V.Above data show and adopt flat band voltage that 400 degrees centigrade of 40 minutes metal electrodes of hafnium silicon oxygen nitrogen medium form after annealings (d) near ideal value, are illustrated in that interface charge is minimum in the case.
Fig. 3 shows the current-voltage curve that adopts hafnium oxynitride medium and the tantalum nitride gate electrode-gate medium-germanium electric capacity that adopts the hafnium silicon oxygen nitrogen medium.Annealing conditions after metal electrode forms be 400 degrees centigrade 40 minutes.The hafnium oxynitride that is calculated by sputter rate and the thickness of hafnium silicon oxygen nitrogen are respectively 75 dusts and 30 dusts, and the equivalent oxide thickness of being calculated by the accumulation area C meter is respectively 24 dusts and 22 dusts.From figure, can draw, adopt the electric capacity of hafnium silicon oxygen nitrogen medium to have littler gate leakage current.When the gate electrode bias voltage is 1V, adopt the hafnium oxynitride medium and the gate leakage current of the electric capacity that adopts the hafnium silicon oxygen nitrogen medium to be respectively 1.10 * 10
-2Every square centimeter and 9.13 * 10 of ampere
-4Every square centimeter of ampere.Adopt the electric capacity of hafnium silicon oxygen nitrogen medium to have littler gate leakage current.
Above-described specific embodiment; The object of the invention, technical scheme and beneficial effect have been carried out further explain, and institute it should be understood that the above is merely specific embodiment of the present invention; Be not limited to the present invention; All within spirit of the present invention and principle, any modification of being made, be equal to replacement, improvement etc., all should be included within protection scope of the present invention.
Claims (9)
1. a method that on the germanium substrate, prepares Metal-oxide-semicondutor electric capacity is characterized in that, this method is employed in the hafnium base high dielectric constant and mixes element silicon, specifically comprises:
Step 1: clean germanium wafer;
Step 2:, and repeat 1 to 10 deposit multilayer silicon nitride and hafnium nitride lamination at the method that adopts the radio frequency magnetron reactive sputtering on the germanium wafer after the cleaning deposition silicon nitride film and hafnium nitride film successively in the atmosphere of argon gas and nitrogen;
Step 3: rapid thermal annealing forms the hafnium silicon oxygen nitrogen medium in the atmosphere of nitrogen;
Step 4: the figure that on the germanium wafer after the annealing, forms photoresist;
Step 5: the method depositing metal electrode material that adopts the radio frequency magnetron reactive sputtering;
Step 6: metal electrode material is peeled off to form electrode pattern;
Step 7: at the back spatter layer of metal aluminium of germanium substrate to reduce the contact resistance at the back side;
Step 8: in the atmosphere of nitrogen in boiler tube annealed metalization.
2. the method that on the germanium substrate, prepares Metal-oxide-semicondutor electric capacity according to claim 1 is characterized in that, the step of cleaning germanium wafer described in the step 1 comprises:
In acetone, soaked 5～20 minutes; Soaked deionized water rinsing, oxidation 10～120 seconds in hydrogen peroxide solution then in the ethanol 5～20 minutes; Deionized water rinsing; Then in hydrochloric acid solution, corroded 30～300 seconds deionized water rinsing, hydrogen peroxide solution oxidation and hydrochloric acid solution corrosion repetition 2 to 5 times; Deionized water rinsing dries up with nitrogen then.
3. the method that on the germanium substrate, prepares Metal-oxide-semicondutor electric capacity according to claim 2; It is characterized in that; In said hydrogen peroxide solution and the hydrochloric acid solution, the percent by volume of hydrogen peroxide solution is 2% to 10%, and the percent by volume of hydrochloric acid solution is 5% to 20%.
4. the method that on the germanium substrate, prepares Metal-oxide-semicondutor electric capacity according to claim 1; It is characterized in that; At the method that adopts the radio frequency magnetron reactive sputtering on the germanium wafer after the cleaning deposition silicon nitride film and hafnium nitride film successively in the atmosphere of argon gas and nitrogen, the step that repeats repeatedly deposit multilayer silicon nitride and hafnium nitride lamination comprises described in the step 2:
Before sputter, the sputtering chamber vacuum is evacuated to 1 * 10
-6Hold in the palm 1 * 10
-7Between the holder, charge into nitrogen and argon gas, the volume ratio of the two is between 1: 20 to 6: 20, sputter silicon target and hafnium target successively then, and deposition silicon nitride film and hafnium nitride film repeat 1 to 10 deposit multilayer silicon nitride and hafnium nitride lamination.
5. the method that on the germanium substrate, prepares Metal-oxide-semicondutor electric capacity according to claim 4; It is characterized in that; In described silicon nitride film and the hafnium nitride film thickness of silicon nitride film be 2 dusts to 6 dusts, the thickness of hafnium nitride film is that 2 dusts are to 9 dusts.
6. the method that on the germanium substrate, prepares Metal-oxide-semicondutor electric capacity according to claim 1 is characterized in that, described in the step 3 in the atmosphere of nitrogen the step of rapid thermal annealing comprise:
Rapid thermal annealing 30 seconds to 120 seconds under 300 degrees centigrade to 600 degrees centigrade the temperature in the atmosphere of nitrogen.
7. the method that on the germanium substrate, prepares Metal-oxide-semicondutor electric capacity according to claim 1 is characterized in that, adopts the step of the method depositing metal electrode material of radio frequency magnetron reactive sputtering to comprise described in the step 5:
Before sputter, the sputtering chamber vacuum is evacuated to 1 * 10
-6Hold in the palm 1 * 10
-7Between the holder, charge into nitrogen and argon gas, the volume ratio of the two is between 1: 20 to 6: 20, sputter tantalum target or titanium target then, and deposit tantalum nitride electrode film or titanium nitride electrode film, its thickness are that 500 dusts are to 2000 dusts.
8. the method that on the germanium substrate, prepares Metal-oxide-semicondutor electric capacity according to claim 1 is characterized in that, the back spatter layer of metal aluminium at the germanium substrate described in the step 7 comprises with the step that reduces back side contact resistance:
At the back spatter layer of metal aluminium of germanium substrate, thickness is that 2000 dusts are to 10000 dusts.
9. the method that on the germanium substrate, prepares Metal-oxide-semicondutor electric capacity according to claim 1 is characterized in that, described in the step 8 in the atmosphere of nitrogen in boiler tube the step of annealed metalization comprise:
In the atmosphere of nitrogen, under 300 degrees centigrade to 500 degrees centigrade condition, annealing is 20 minutes to 60 minutes in boiler tube.
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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 |
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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 |
Non-Patent Citations (1)
| Title |
|---|
| Hu Aibin and Xu Qiuxia.Effects of silicon nitride diffusion barrier on germanium MOS capacitors with HfON gate dielectrics.《Journal of semiconductors》.2009,第30卷(第10期),第104002-1页-第104002-5页. * |
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