CN101800178B - Preparation method of hafnium silicon aluminum oxygen nitrogen high-dielectric constant gate dielectric - Google Patents
Preparation method of hafnium silicon aluminum oxygen nitrogen high-dielectric constant gate dielectric Download PDFInfo
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- CN101800178B CN101800178B CN2009100776238A CN200910077623A CN101800178B CN 101800178 B CN101800178 B CN 101800178B CN 2009100776238 A CN2009100776238 A CN 2009100776238A CN 200910077623 A CN200910077623 A CN 200910077623A CN 101800178 B CN101800178 B CN 101800178B
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Abstract
The invention provides a preparation method of a hafnium silicon aluminum oxygen nitrogen high-dielectric constant gate dielectric, which comprises the steps of: deposing aluminum nitride thin films at the upper surface and the lower surface of a hafnium silicon aluminum oxygen nitrogen high-dielectric constant gate dielectric; and forming the hafnium silicon aluminum oxygen nitrogen high-dielectric constant gate dielectric by means of high temperature annealing. The method specifically comprises the steps of: washing a silicon wafer; oxygenizing the washed silicon wafer before depositing; depositing the hafnium silicon aluminum oxygen nitrogen high-dielectric constant gate dielectric on the oxygenized silicon wafer; ultrasonically washing the hafnium silicon aluminum oxygen nitrogen high-dielectric constant gate dielectric-deposited silicon wafer; depositing and annealing the silicon wafer which forms into a metal gate; and splashing the aluminum at the back of the silicon wafer and performing alloy treatment. The preparation method solves the problems that the electricity leakage of the gate dielectric is quick raised and the power consumption is seriously enlarged along with the reduction of the depth of the gate dielectric of a small-size device, and is good for adjusting the work function of a semiconductor device of a P type metal oxide.
Description
Technical field
The present invention relates to nanometer feature sizes semiconductor device preparing technical field; Relate in particular to a kind of preparation method who is used for hafnium silicon aluminum oxygen nitrogen (HfSiAlON) high-dielectric-coefficient grid medium of nanoscale P-type mos device manufacturing; Bring the gate medium electric leakage sharply to rise and the serious problem that increases of power consumption to solve, help solving the problem of P-type mos device metal gate work function adjustment simultaneously along with the attenuate of small size device grid medium thickness.
Background technology
Over more than 40 year, integrated circuit technique is by the sustainable development of mole law, and characteristic size is constantly dwindled, and integrated level improves constantly, and function is more and more stronger.Along with constantly reducing of device size, gate oxide thickness is attenuate thereupon.
At present, the characteristic size of metal oxide semiconductor transistor (MOSFET) has got into inferior 50 nanometers, and gate oxide thickness has been reduced to below 1.2 nanometers.Gate oxide is so thin, if still adopt conventional oxidation silicon or nitride-monox gate medium, the direct Tunneling electric current sharply increases the exponentially rule.
According to ITRS (ITRS2007) in 2007 prediction, by 2008, plane body silicon device nitride-monox gate medium leakage current will reach 9 * 10
2A/cm
2, surpass the limit that device can bear, must adopt high dielectric constant material as gate medium.Its reason is, under same equivalent oxide thickness, high dielectric constant material has thicker physical thickness, makes that the direct Tunneling electric current reduces greatly between grid and raceway groove, and power consumption significantly reduces.
2007, Intel company began to introduce high-dielectric-coefficient grid medium and metal gate technique in 45 nm technology node, and was applied to the making of its new types of processors.Large-scale semiconductor company such as AMD and IBM also begins the research and development emphasis is transferred to high-dielectric-coefficient grid medium and metal gate technique.
Though obtained a lot of achievements and begun to be applied to industry in high-dielectric-coefficient grid medium/metal gate research field in recent years, but still existed many problem needs further to improve.Follow development of semiconductor, the high-dielectric-coefficient grid medium material is had higher requirement, for example high dielectric constant, good thermal stability and reliability etc.Simultaneously, require the employing of high-dielectric-coefficient grid medium material to help combining with metal gate technique.Therefore, the development of high-dielectric-coefficient grid medium/metal gate technique shoulders heavy responsibilities.
In order to obtain appropriate threshold voltage, the work function that requires the PMOS metal gate material usually is near 5.2eV, yet it is good to have the metal material chemical stability of high work function like this, is difficult to etching, and very expensive, for example platinum and gold etc.Discover, in gate medium, introduce the adjustment that aluminium helps PMOS metal gate work function.Based on this thought, the present invention proposes a kind of preparation method of hafnium silicon aluminum oxygen nitrogen high-dielectric constant gate dielectric, and adopt the method for sputtering deposit to prepare.
Summary of the invention
The technical problem that (one) will solve
Main purpose of the present invention is to provide a kind of preparation method of hafnium silicon aluminum oxygen nitrogen high-dielectric constant gate dielectric; Bring the gate medium electric leakage sharply to rise and the serious problem that increases of power consumption to solve along with the attenuate of small size device grid medium thickness; Simultaneously; This technology helps promoting the metal gate electrode flat band voltage to move to forward, promptly helps the adjustment of PMOS metal gate work function.
(2) technical scheme
For achieving the above object; The invention provides a kind of preparation method of hafnium silicon aluminum oxygen nitrogen high-dielectric constant gate dielectric; This method is the upper and lower surfaces place deposit aluminium nitride film at hafnium silicon aluminum oxygen nitrogen high-dielectric constant gate dielectric; Form hafnium silicon aluminum oxygen nitrogen high-dielectric constant gate dielectric through high annealing again, this method comprises:
Cleaning silicon chip;
Silicon chip to after cleaning carries out oxidation before deposition;
Deposit hafnium silicon aluminum oxygen nitrogen high-dielectric constant gate dielectric on the silicon chip after the oxidation;
To deposit the silicon chip of hafnium silicon aluminum oxygen nitrogen high-dielectric constant gate dielectric carry out ultrasonic cleaning;
Silicon chip to after cleaning carries out the deposit after annealing;
On the silicon chip after the annealing, form metal gate;
Silicon chip to forming metal gate carries out the deposit after annealing;
The back side is spattered aluminium and is carried out alloy treatment.
In the such scheme, the step of said cleaning silicon chip comprises: clean with conventional method earlier, at room temperature soaked 1 to 10 minute with hydrofluoric acid/isopropanol, deionized water rinsing dries then.
In the such scheme, said conventional method is in 3# liquid, to clean 10 minutes, in 1# liquid, cleans 5 minutes then; Said 3# liquid is that volume ratio is (3～5): 1 H
2SO
4+ H
2O
2Solution, said 1# liquid are that volume ratio is (1～0.7): 1: 5 NH
4OH+H
2O
2+ H
2O solution.
In the such scheme, the said step that silicon chip after cleaning is carried out oxidation before deposition comprises: rapid thermal oxidation 30 to 120 seconds under 600 to 800 ℃ of temperature in containing the nitrogen of trace oxygen generates the oxide layer of 5 to 8 dusts.
In the such scheme, said on the silicon chip after the oxidation step of deposit hafnium silicon aluminum oxygen nitrogen high-dielectric constant gate dielectric comprise: adopt reactive magnetron sputtering technology, sputtering power is 200 to 600W, and operating pressure is (2～8) * 10
-3Torr; Alternating sputtering aluminium target, hafnium target and silicon target in argon gas and nitrogen; Deposit successively forms the hafnium silicon aluminum oxygen nitrogen high-dielectric constant gate dielectric film; Wherein aluminium nitride mainly is distributed in the upper and lower interface of hafnium silicon aluminum oxygen nitrogen high-dielectric constant gate dielectric film, and adjustment sputtering power and time can change the thickness and the component of film.
In the such scheme, the step of said ultrasonic cleaning comprises: adopt acetone ultrasonic cleaning 5～10 minutes, and absolute ethyl alcohol ultrasonic cleaning 5～10 minutes, deionized water rinsing dries.
In the such scheme, the step of said deposit after annealing comprises: under nitrogen protection, rapid thermal annealing is 5 to 90 seconds under 500 to 1000 ℃ of temperature.
In the such scheme, the step of said formation metal gate comprises: at Ar/N
2Mixed atmosphere in the sputter tantalum target, deposit forms tantalum nitride TaN metal gate, wherein TaN thickness is 300 to 1500 dusts.
In the such scheme, the step of this said metal gate deposit post growth annealing comprises: under nitrogen protection, rapid thermal annealing is 2 to 20 seconds under 700 to 1000 ℃ of temperature.
In the such scheme, the step that the said back side is spattered aluminium and carried out alloy treatment comprises: in Ar gas, adopt direct current sputtering technology back spatter Al electrode, the Al thickness of electrode is 5000 to 10000 dusts; Then, alloy annealing 30 to 60 minutes under 350 to 500 ℃ of temperature under nitrogen protection.
(3) beneficial effect
Adopt the preparation method of hafnium silicon aluminum oxygen nitrogen high-dielectric constant gate dielectric provided by the invention; Can obtain to have the gate dielectric material of high dielectric constant; Solution brings the gate medium electric leakage sharply to rise and the serious problem that increases of power consumption along with the attenuate of small size device grid medium thickness, the introducing of Al simultaneously helps the adjustment of P-type mos device metal gate work function.
In addition; Adopting sputtering deposit technology preparation hafnium silicon aluminum oxygen nitrogen high-dielectric constant gate dielectric also is one of innovative point of this invention; And the present invention has low, the simple to operate and output advantages of higher of cost, utilizes sputtering deposit technology preparation gate dielectric membrane with high dielectric coefficient to help promoting the development of its industrialization.
The preparation method of this hafnium silicon aluminum oxygen nitrogen high-dielectric constant gate dielectric provided by the invention; Under same equivalent oxide thickness; High-dielectric-coefficient grid medium has the physical thickness thicker than nitride-monox gate medium, has solved along with the attenuate of small size device grid medium thickness to bring the gate medium electric leakage sharply to rise and the serious problem that increases of power consumption, simultaneously because the existence of Al; The flat band voltage of metal gate is moved to forward, help the adjusting of PMOS metal gate work function.
The preparation method's of this hafnium silicon aluminum oxygen nitrogen high-dielectric constant gate dielectric provided by the invention advantage is: (1) Al has an adjustment that is beneficial to PMOS metal gate work function; (2) SiOx makes the interface good at the interface, helps improving the mobility of device; (3) sputtering technology is simple, is easy to obtain as thin as a wafer and the uniform film of thickness, and is with low cost.
Description of drawings
Below in conjunction with accompanying drawing and embodiment the present invention is further specified:
Fig. 1 is the method flow diagram that hafnium provided by the invention prepares silicon aluminum oxygen nitrogen high-dielectric constant gate dielectric.
Fig. 2 is the sketch map of hafnium silicon aluminum oxygen nitrogen high-dielectric constant gate dielectric structure provided by the invention; Wherein, Fig. 2 (a) is the sketch map of hafnium silicon aluminum oxygen nitrogen high-dielectric constant gate dielectric structure before the annealing, and Fig. 2 (b) is the sketch map of annealing back hafnium silicon aluminum oxygen nitrogen high-dielectric constant gate dielectric structure;
Fig. 3 is the contrast sketch map that utilizes " capacitance-voltage (C-V) " test curve of HfSiAlON/TaN gate dielectric structure electric capacity that the present invention prepares and HfSiON/TaN grid structure capacitive.
Fig. 4 is the leakage current characteristic (I that utilizes the HfSiAlON high-dielectric-coefficient grid medium that the present invention prepares
g-V
g) curve.
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 magnetron sputtering technique to prepare hafnium silicon aluminum oxygen nitrogen (HfSiAlON) high-dielectric-coefficient grid medium; The preparation method is: after silicon chip is through conventional the cleaning; Generate for suppressing natural oxide, adopt under hydrofluoric acid/isopropanol room temperature and soak deionized water rinsing; Advance stove after the drying immediately, with rapid thermal oxidation growth interface SiO
xLayer; In the mixed atmosphere of argon gas and nitrogen, utilize magnetron sputtering technique sputtering deposit AlN film; In the mixed atmosphere of argon gas and nitrogen, utilize magnetron sputtering technique alternating sputtering hafnium (Hf) target and silicon (Si) target then, deposit forms the HfSiON gate dielectric membrane with high dielectric coefficient, deposit one deck aluminium nitride film again on the HfSiON gate medium; Carry out quick thermal annealing process after the deposit and form the HfSiAlON high-dielectric-coefficient grid medium; Form metal gate electrode then, aluminium and alloy are spattered in the back side, so that electrical measurement.
As shown in Figure 1; Fig. 1 is the method flow diagram that hafnium provided by the invention prepares silicon aluminum oxygen nitrogen high-dielectric constant gate dielectric; This method is the upper and lower surfaces place deposit aluminium nitride film at hafnium silicon aluminum oxygen nitrogen high-dielectric constant gate dielectric; Form hafnium silicon aluminum oxygen nitrogen high-dielectric constant gate dielectric through high annealing again, this method comprises:
Step 1: cleaning silicon chip;
In this step, clean with conventional method earlier, at room temperature soaked 1 to 10 minute with hydrofluoric acid/isopropanol again, deionized water rinsing dries twice then, advances stove immediately; Said conventional method is in 3# liquid, to clean 10 minutes, in 1# liquid, cleans 5 minutes then; Said 3# liquid is that volume ratio is 5: 1 H
2SO
4+ H
2O
2Solution, said 1# liquid are that volume ratio is 0.7: 1: 5 NH
4OH+H
2O
2+ H
2O solution.
Step 2: the silicon chip to after cleaning carries out oxidation before deposition;
In this step, rapid thermal oxidation 30 to 120 seconds under 600 to 800 ℃ of temperature in containing the nitrogen of trace oxygen generates the oxide layer of 5 to 8 dusts.
Step 3: deposit hafnium silicon aluminum oxygen nitrogen high-dielectric constant gate dielectric on the silicon chip after the oxidation;
In this step, deposit aluminium nitride film as thin as a wafer on the silicon chip after the oxidation at first, sputtering power are 300 to 600W, and operating pressure is 2～5 * 10
-3Torr, at argon gas and nitrogen, the sputtered aluminum target, deposit forms the AlN film, and adjustment sputtering power and time can change the thickness of film; Then, be deposited with deposit hafnium silicon oxygen nitrogen gate dielectric membrane with high dielectric coefficient on the silicon chip of aluminium nitride, sputtering power is 300 to 500W, and operating pressure is 5 * 10
-3Torr, in argon gas and nitrogen, alternating sputtering hafnium target and silicon target, deposit successively forms HfSiON high-k gate dielectric film, and adjustment sputtering power and time can change the thickness and the component of film; At last, deposit one deck aluminium nitride film as thin as a wafer again on the hafnium silicon oxygen nitrogen gate medium.
Step 4: to deposit the silicon chip of hafnium silicon aluminum oxygen nitrogen high-dielectric constant gate dielectric carry out ultrasonic cleaning;
In this step, adopt acetone ultrasonic cleaning 5～10 minutes, absolute ethyl alcohol ultrasonic cleaning 5～10 minutes, deionized water rinsing dries.
Step 5: the silicon chip to after cleaning carries out the deposit after annealing;
In this step, under nitrogen protection, rapid thermal annealing is 5 to 90 seconds under 500 to 1000 ℃ of temperature.
Step 6: on the silicon chip after the annealing, form metal gate;
In this step, at Ar/N
2Mixed atmosphere in the sputter tantalum target, deposit forms tantalum nitride TaN metal gate, TaN thickness is 300 to 1500 dusts.
Step 7: the silicon chip to forming metal gate carries out the deposit after annealing;
In this step, under nitrogen protection, rapid thermal annealing is 2 to 20 seconds under 700 to 1100 ℃ of temperature.
Step 8: the back side is spattered aluminium and is carried out alloy treatment;
In this step, it is in Ar gas, to adopt direct current sputtering technology back spatter Al electrode that aluminium is spattered at the said back side, and the Al thickness of electrode is 5000 to 10000 dusts; Said alloy is an alloy annealing 30 to 60 minutes under 350 to 500 ℃ of temperature under nitrogen protection.
Shown in Figure 2 is the sketch map of hafnium silicon aluminum oxygen nitrogen high-dielectric constant gate dielectric structure provided by the invention, and wherein, Fig. 2 (a) is the sketch map of hafnium silicon aluminum oxygen nitrogen high-dielectric constant gate dielectric structure before the annealing, and this structure comprises:
The 101:TaN metal gate electrode;
The 102:AlN film;
103:HfSiON high-k gate dielectric film;
The 104:AlN film;
105:SiO
2Film;
The 106:Si substrate.
Fig. 2 (b) is the sketch map of annealing back hafnium silicon aluminum oxygen nitrogen high-dielectric constant gate dielectric structure, and this structure comprises:
The 107:TaN metal gate electrode;
108:HfSiAlON high-k gate dielectric film;
109:SiO
2Film;
The 110:Si substrate.
Fig. 3 shows the contrast of " capacitance-voltage (the C-V) " test curve that utilizes HfSiAlON/TaN gate dielectric structure electric capacity that the present invention prepares and HfSiON/TaN grid structure capacitive.The flat band voltage V of HfSiON/TaN grid structure capacitive
FbBe-0.107V the flat band voltage V of HfSiAlON/TaN gate dielectric structure electric capacity
FbBe 0.206V because the introducing of Al, cause flat band voltage to positive excursion 0.313V.
Fig. 4 shows the leakage current characteristic (I that utilizes the HfSiAlON high-dielectric-coefficient grid medium that the present invention prepares
g-V
g) curve.HfSiAlON gate medium leakage current density is 3.89 * 10
-3A/cm
2(V
g=V
Fb+ 1V).
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. the preparation method of a hafnium silicon aluminum oxygen nitrogen high-dielectric constant gate dielectric; It is characterized in that; This method is the upper and lower surfaces place deposit aluminium nitride film at the hafnium silicon oxygen nitrogen high-dielectric-coefficient grid medium, forms hafnium silicon aluminum oxygen nitrogen high-dielectric constant gate dielectric through high annealing again, and this method comprises:
Cleaning silicon chip;
Silicon chip to after cleaning carries out oxidation before deposition;
Deposit aluminium nitride film on the silicon chip after the oxidation;
Deposit hafnium silicon oxygen nitrogen gate dielectric membrane with high dielectric coefficient on said aluminium nitride film;
Deposit aluminium nitride film on said hafnium silicon oxygen nitrogen gate dielectric membrane with high dielectric coefficient;
To deposit the silicon chip of hafnium silicon aluminum oxygen nitrogen high-dielectric constant gate dielectric film carry out ultrasonic cleaning;
Silicon chip after cleaning is carried out the deposit after annealing to form hafnium silicon aluminum oxygen nitrogen high-dielectric constant gate dielectric, and this annealing is under nitrogen protection, and rapid thermal annealing is 5 to 90 seconds under 500 to 1000 ℃ of temperature;
On the silicon chip after the annealing, form metal gate;
Silicon chip to forming metal gate carries out the deposit after annealing;
The back side is spattered aluminium and is carried out alloy treatment.
2. the preparation method of hafnium silicon aluminum oxygen nitrogen high-dielectric constant gate dielectric according to claim 1 is characterized in that, the step of said cleaning silicon chip comprises:
Clean with conventional method earlier, the mixed solution with hydrofluoric acid and isopropyl alcohol and water at room temperature soaked 1 to 10 minute again, and deionized water rinsing dries then.
3. the preparation method of hafnium silicon aluminum oxygen nitrogen high-dielectric constant gate dielectric according to claim 2 is characterized in that, said conventional method is in 3# liquid, to clean 10 minutes, in 1# liquid, cleans 5 minutes then; Said 3# liquid is that volume ratio is (3～5): 1 H
2SO
4+ H
2O
2Solution, said 1# liquid are that volume ratio is (1～0.7): 1: 5 NH
4OH+H
2O
2+ H
2O solution.
4. the preparation method of hafnium silicon aluminum oxygen nitrogen high-dielectric constant gate dielectric according to claim 1 is characterized in that, the said step that silicon chip after cleaning is carried out oxidation before deposition comprises:
Rapid thermal oxidation 30 to 120 seconds under 600 to 800 ℃ of temperature in containing the nitrogen of trace oxygen generates the oxide layer of 5 to 8 dusts.
5. the preparation method of hafnium silicon aluminum oxygen nitrogen high-dielectric constant gate dielectric according to claim 1 is characterized in that,
Said on the silicon chip after the oxidation deposit aluminium nitride film, sputtering power is 300 to 600W, operating pressure is 2～5 * 10
-3Torr, at argon gas and nitrogen, the sputtered aluminum target, deposit forms the AlN film;
Said on aluminium nitride film deposit hafnium silicon oxygen nitrogen gate dielectric membrane with high dielectric coefficient, sputtering power is 300 to 500W, operating pressure is 5 * 10
-3Torr, in argon gas and nitrogen, alternating sputtering hafnium target and silicon target, deposit successively forms HfSiON high-k gate dielectric film.
6. the preparation method of hafnium silicon aluminum oxygen nitrogen high-dielectric constant gate dielectric according to claim 1 is characterized in that, the step of said ultrasonic cleaning comprises:
Adopt acetone ultrasonic cleaning 5～10 minutes, absolute ethyl alcohol ultrasonic cleaning 5～10 minutes, deionized water rinsing dries.
7. the preparation method of hafnium silicon aluminum oxygen nitrogen high-dielectric constant gate dielectric according to claim 1 is characterized in that, the step of said formation metal gate comprises:
At Ar/N
2Mixed atmosphere in the sputter tantalum target, deposit forms tantalum nitride TaN metal gate, wherein TaN thickness is 300 to 1500 dusts.
8. the preparation method of hafnium silicon aluminum oxygen nitrogen high-dielectric constant gate dielectric according to claim 1 is characterized in that, the step of this said metal gate deposit post growth annealing comprises:
Under nitrogen protection, rapid thermal annealing is 2 to 20 seconds under 700 to 1000 ℃ of temperature.
9. the preparation method of hafnium silicon aluminum oxygen nitrogen high-dielectric constant gate dielectric according to claim 1 is characterized in that, the step that the said back side is spattered aluminium and carried out alloy treatment comprises:
In Ar gas, adopt direct current sputtering technology back spatter Al electrode, the Al thickness of electrode is 5000 to 10000 dusts; Then, alloy annealing 30 to 60 minutes under 350 to 500 ℃ of temperature under nitrogen protection.
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| US8822292B2 (en) | 2011-11-23 | 2014-09-02 | Institute of Microelectronics, Chinese Academy of Sciences | Method for forming and controlling molecular level SiO2 interface layer |
| CN103137460B (en) * | 2011-11-23 | 2016-02-10 | 中国科学院微电子研究所 | A kind of molecular scale interface SiO 2formation and control method |
| CN103545182B (en) * | 2012-07-12 | 2017-03-29 | 中国科学院微电子研究所 | A kind of low work function metal gate forming method |
| CN104112680A (en) * | 2013-04-22 | 2014-10-22 | 无锡华润上华半导体有限公司 | Semiconductor device back manufacturing process |
| CN105869992A (en) * | 2016-03-31 | 2016-08-17 | 国网山东省电力公司夏津县供电公司 | Preparation method for novel hafnium-silicon-tantalum-oxygen-nitrogen high-dielectric-constant gate dielectric |
| CN112002804A (en) * | 2020-09-02 | 2020-11-27 | 北京理工大学 | High-k gate dielectric material and preparation method and application thereof |
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