CN100543941C - The ultra-thin HfO of a kind of preparation 2Or ZrO 2The soft chemical method of gate dielectric membrane - Google Patents
The ultra-thin HfO of a kind of preparation 2Or ZrO 2The soft chemical method of gate dielectric membrane Download PDFInfo
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- 238000000034 method Methods 0.000 title claims abstract description 38
- 238000002360 preparation method Methods 0.000 title claims abstract description 28
- 239000000126 substance Substances 0.000 title claims abstract description 14
- 239000012528 membrane Substances 0.000 title claims abstract description 11
- 239000000758 substrate Substances 0.000 claims abstract description 50
- 238000000137 annealing Methods 0.000 claims abstract description 9
- 239000010408 film Substances 0.000 claims description 54
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 claims description 38
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 37
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 27
- 229910007926 ZrCl Inorganic materials 0.000 claims description 22
- 238000004140 cleaning Methods 0.000 claims description 17
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 16
- 239000008367 deionised water Substances 0.000 claims description 16
- 229910021641 deionized water Inorganic materials 0.000 claims description 16
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 15
- 230000007062 hydrolysis Effects 0.000 claims description 11
- 238000006460 hydrolysis reaction Methods 0.000 claims description 11
- 239000004065 semiconductor Substances 0.000 claims description 10
- 239000010409 thin film Substances 0.000 claims description 9
- 238000010521 absorption reaction Methods 0.000 claims description 8
- 238000013019 agitation Methods 0.000 claims description 8
- 239000011248 coating agent Substances 0.000 claims description 8
- 238000000576 coating method Methods 0.000 claims description 8
- 239000000843 powder Substances 0.000 claims description 8
- 229920006395 saturated elastomer Polymers 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- 239000003085 diluting agent Substances 0.000 claims description 7
- 229910052757 nitrogen Inorganic materials 0.000 claims description 7
- 238000005516 engineering process Methods 0.000 abstract description 9
- 238000004377 microelectronic Methods 0.000 abstract description 4
- 239000002243 precursor Substances 0.000 abstract description 4
- DKPJKHVUKFQGCZ-UHFFFAOYSA-F [Cl-].[Cl-].[Cl-].[Cl-].[Cl-].[Cl-].[Cl-].[Cl-].[Zr+4].[Hf+4] Chemical compound [Cl-].[Cl-].[Cl-].[Cl-].[Cl-].[Cl-].[Cl-].[Cl-].[Zr+4].[Hf+4] DKPJKHVUKFQGCZ-UHFFFAOYSA-F 0.000 abstract 1
- KQHQLIAOAVMAOW-UHFFFAOYSA-N hafnium(4+) oxygen(2-) zirconium(4+) Chemical compound [O--].[O--].[O--].[O--].[Zr+4].[Hf+4] KQHQLIAOAVMAOW-UHFFFAOYSA-N 0.000 abstract 1
- 238000004321 preservation Methods 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 21
- 238000000427 thin-film deposition Methods 0.000 description 8
- 239000000203 mixture Substances 0.000 description 7
- 239000000463 material Substances 0.000 description 6
- 238000001228 spectrum Methods 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Inorganic materials [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- 229910018557 Si O Inorganic materials 0.000 description 3
- 229910008045 Si-Si Inorganic materials 0.000 description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- 229910006411 Si—Si Inorganic materials 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 229910044991 metal oxide Inorganic materials 0.000 description 3
- 150000004706 metal oxides Chemical class 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 239000010703 silicon Substances 0.000 description 3
- 241000588731 Hafnia Species 0.000 description 2
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 2
- 229910004298 SiO 2 Inorganic materials 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000003989 dielectric material Substances 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 229910052735 hafnium Inorganic materials 0.000 description 2
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 description 2
- CJNBYAVZURUTKZ-UHFFFAOYSA-N hafnium(IV) oxide Inorganic materials O=[Hf]=O CJNBYAVZURUTKZ-UHFFFAOYSA-N 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 230000003746 surface roughness Effects 0.000 description 2
- 150000004703 alkoxides Chemical class 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 238000005137 deposition process Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 238000011010 flushing procedure Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229910000449 hafnium oxide Inorganic materials 0.000 description 1
- PDPJQWYGJJBYLF-UHFFFAOYSA-J hafnium tetrachloride Chemical compound Cl[Hf](Cl)(Cl)Cl PDPJQWYGJJBYLF-UHFFFAOYSA-J 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 230000000873 masking effect Effects 0.000 description 1
- 229910001510 metal chloride Inorganic materials 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- QPJSUIGXIBEQAC-UHFFFAOYSA-N n-(2,4-dichloro-5-propan-2-yloxyphenyl)acetamide Chemical compound CC(C)OC1=CC(NC(C)=O)=C(Cl)C=C1Cl QPJSUIGXIBEQAC-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 230000005641 tunneling Effects 0.000 description 1
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 description 1
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Abstract
The invention discloses the ultra-thin HfO of a kind of preparation
2Or ZrO
2The soft chemical method of gate dielectric membrane, by a kind of simple and feasible process route, successfully prepared and had better stability and inhomogeneity hafnium chloride (zirconium) precursor colloidal sol, this colloidal sol has the long preservation life-span, uses this precursor colloidal sol, passes through softening method, under room temperature on the Si substrate, successfully prepare ultra-thin hafnium oxide (zirconium) film of surfacing,, obtained to have the gate dielectric membrane of excellent electric property by after annealing.The method preparation technology is simple, and is with low cost, in the unique advantage of microelectronic, has important application prospects.
Description
One, technical field
The present invention relates to a kind of preparation ultra-thin metal oxide (HfO
2Or ZrO
2) method of gate dielectric membrane, specifically be that a kind of employing soft chemical method prepares above-mentioned ultra-thin HfO
2Or ZrO
2The method of gate dielectric membrane.
Two, background technology
Along with developing rapidly of semiconductor technology, just according to Moore's Law, constantly dwindle as the characteristic size of the metal-oxide-semiconductor field (MOSFETs) of silica-based microelectronics core devices.But, traditional SiO
2Gate dielectric material can't overcome the influence that the MOSFET device feature size dwindles the quantum tunneling effect that is brought, and works as SiO
2Thickness when being reduced to 1nm, grid leakage current increases rapidly, can cause device reliability to worsen, can't operate as normal.In order further to improve the integrated level of microelectronic component, must consider to substitute traditional SiO with having high-k (high-k) gate dielectric material
2Layer.Hafnium oxide, zirconia film have bigger dielectric constant (k=20～25) and energy gap (Eg～5.6eV) and the thermodynamic stability of the excellence that contacts with Si, therefore becoming one of most promising candidate material of grid medium with high dielectric of future generation, also is the focus of current high-k investigation of materials.
So-called soft chemical method (soft chemical method) is meant the liquid-phase mixing by reaction raw materials, makes the metallic element high degree of dispersion under lower reaction temperature and relatively mild chemical environment, carries out the method that chemical reaction prepares material step by step.As sol-gel (Sol-Gel) process of synthesizing inorganic pottery, glass material under the normal temperature and pressure, low temperature liquid phase prepared in reaction nano structural material etc. all belong to softening method.But in general colloidal sol-gel method, metal precursor colloidal sol generally adopts metal alkoxide, its process for preparation is complicated and unstable, hydrolysis easily, and be difficult to find most suitable solvent to make more evenly dispersion, stable sols, influenced the industrial applications of the method.
Three, summary of the invention
Technical problem to be solved by this invention provides a kind of special so-gel (Sol-Gel) method and comes depositing ultrathin metal oxide (HfO
2Or ZrO
2) method of gate dielectric membrane.Preparation technology is simple for this method, and is with low cost.
For achieving the above object, the ultra-thin HfO of preparation of the present invention
2Or ZrO
2The soft chemical method of gate dielectric membrane mainly comprises following three steps
(1) HfCl
4(or ZrCl
4) preparing process of colloidal sol
Synthesis material: anhydrous hafnium tetrachloride (HfCl
4) or anhydrous zirconium chloride (ZrCl
4); Absolute ethyl alcohol (ethanol); Acetylacetone,2,4-pentanedione (acetylacetone).
Stable HfCl
4(or ZrCl) colloidal sol synthesis technique: synthesis process flow diagram as shown in Figure 1, whole process for preparation carries out in the hand of nitrogen atmosphere behaviour case, to avoid the moisture in the environment.Get the anhydrous HfCl of 0.005～0.02mol
4(or anhydrous ZrCl
4) powder dissolves in 20～40ml absolute ethyl alcohol, stir it is dissolved fully; 3～6ml acetylacetone,2,4-pentanedione and 10～20ml absolute ethyl alcohol are mixed.Above two kinds of solution are mixed, take out the solution for preparing then from hand behaviour case, at room temperature magnetic agitation is 4～7 hours, obtains the stable HfCl that concentration is about 0.1～0.4mol/l
4(or ZrCl
4) colloidal sol.
(2) Si substrate processing technology
After the cleaning of monocrystalline substrate usefulness standard RCA semiconductor cleaning, hydrofluoric acid (HF) solution (volume ratio of hydrofluoric acid and deionized water is 1:8～10) with dilution at room temperature soaked 3～6 minutes again, remove the oxide skin(coating) on monocrystalline substrate surface, because the corrosion of hydrofluoric acid, this moment, the Si substrate surface hung hydrogen bond, was hydrophobicity; At last this Si substrate is put into the hydrogen peroxide (H of 50～80 ℃ 30% weight ratio
2O
2) in sonicated 8～15 minutes.At this moment, the Si substrate surface evenly hangs hydroxyl and (OH), is total hydrophilic.
(3) thin film preparation process:
Its process chart is (ZrO as shown in Figure 2
2Deposition process similarly), this process all can be in air, finish under the room temperature, have four steps: (1) surface is from limiting chemisorbed: the Si substrate is immersed the above-mentioned HfCl for preparing
4Or ZrCl
4Kept in the colloidal sol 3～5 minutes, and made it saturated absorption; (2) flushing: from colloidal sol, take out the Si substrate, clean the surface with absolute ethyl alcohol; (3) hydrolysis: the sample of cleaning is put into deionized water soaked 3～5 minutes, fully hydrolysis generates HfO
2Or ZrO
2(4) dry up: with high pure nitrogen (N
2) dry up sample surfaces.Circulate above step 8～50 time make HfO
2Or ZrO
2Film, afterwards in 400～800 ℃ in nitrogen atmosphere short annealing obtained finished product in 3～5 minutes.
Basic principle of the present invention is: utilize metal chloride colloidal sol that adsorption reaction takes place on hydrophilic substrate, thereby realize the even growth of metal-oxide film.Its technical process is divided into following four steps: 1. the chemisorbed of substrate surface; 2. clean; 3. hydrolysis; 4. dry up.Through research, other masking technique of comparing finds that this method is a kind of more superior chemical method, because it can at room temperature utilize simple equipment, prepares ultra-thin film in large area.
The present invention adopts the technology of simple possible, has successfully prepared to can be used for soft chemical method and prepare ultra-thin HfO
2Or ZrO
2Precursor colloidal sol, and successfully prepared HfO with soft chemical method
2Or ZrO
2Gate dielectric layer.Technology of the present invention is simple, neither need carry out in special environment such as vacuum and high temperature, does not also need expensive equipment, and operability is very strong, and is with low cost, and can select suitable cycle-index, prepares the ultra-thin HfO of different-thickness
2Or ZrO
2Film.The present invention obtains the gate dielectric membrane of equivalent oxide thickness (EOT)＜1 nanometer by optimal preparation technology, and it has a good application prospect in microelectronics industry.
Four, description of drawings
Fig. 1 is HfCl
4(ZrCl
4) synthesis process flow diagram of colloidal sol;
Fig. 2 is that soft chemical method prepares HfO
2The process chart of film;
Fig. 3 is HfO
2The AFM figure of film.Thin film deposition circulation 50 times, afterwards in 500 ℃ AN 5 minutes.RMS＝1.100nm；
Fig. 4 is HfO
2The x-ray photoelectron power spectrum of film.Thin film deposition circulation 50 times, afterwards in 500 ℃ AN 5 minutes, (a) Hf4f wherein, (b) 01s, (c) Si2p;
Fig. 5 is HfO
2Electric capacity-the bias voltage of film (C-V) and leakage current density-bias voltage (J
A-V) characteristic curve.Thin film deposition circulation 50 times, afterwards in 500 ℃ AN 5 minutes;
Fig. 6 is HfO
2The AFM figure of film.Thin film deposition circulation 8 times, afterwards in 800 ℃ AN 5 minutes.RMS＝1.111nm；
Fig. 7 is HfO
2The x-ray photoelectron power spectrum of film.Thin film deposition circulation 8 times, afterwards in 800 ℃ AN 5 minutes, (a) Hf4f wherein, (b) 01s, (c) Si2p;
Fig. 8 is HfO
2Electric capacity-the bias voltage of film (C-V) and leakage current density-bias voltage (J
A-V) characteristic curve.Thin film deposition circulation 8 times, afterwards in 800 ℃ AN 5 minutes;
Fig. 9 HfO
2Electric capacity-the bias voltage of film (C-V) and leakage current density-bias voltage (J
A-V) characteristic curve.Thin film deposition circulation 35 times, afterwards in 800 ℃ AN 3 minutes;
Figure 10 is ZrO
2The x-ray photoelectron power spectrum of film.Thin film deposition circulation 30 times, afterwards in 500 ℃ AN 5 minutes, (a) Zr3d wherein, (b) 01s, (c) Si2p.
Five, embodiment
Embodiment 1:
(1) HfCl
4The preparation of colloidal sol:
In the hand behaviour case of nitrogen atmosphere, get the anhydrous HfCl of 0.01mol
4Powder dissolves in the 30ml absolute ethyl alcohol, stirs it is dissolved fully; 5ml acetylacetone,2,4-pentanedione and 15ml absolute ethyl alcohol are mixed, then above two kinds of solution are mixed; Take out the solution for preparing then from hand behaviour case, at room temperature magnetic agitation is 4～7 hours, obtains concentration and is about 0.2mol/l and stable HfCl
4Colloidal sol;
(2) Si substrate processing:
After the cleaning of monocrystalline substrate usefulness standard RCA semiconductor cleaning, at room temperature soak the oxide skin(coating) (volume ratio of hydrofluoric acid and deionized water is 1:8) of removing the surface in 3～6 minutes with diluent hydrofluoric acid solution again; Then this substrate is put into 30% (mass fraction) hydrogen peroxide sonicated 8～15 minutes of 60 ℃;
(3) thin film preparation process:
At ambient temperature, above-mentioned Si substrate is immersed the HfCl for preparing
4Kept in the colloidal sol 3～5 minutes, and made it saturated absorption; Take out the Si substrate subsequently, and clean the surface with absolute ethyl alcohol; Put into deionized water then and soaked 3～5 minutes, fully hydrolysis generates HfO
2Then dry up sample surfaces with high pure nitrogen; So the above step 50 of circulation time makes HfO
2Film, at last under 500 ℃ in nitrogen atmosphere short annealing made finished product in 5 minutes.
The composition of the above-mentioned finished product that makes and performance parameter:
1. the surface roughness of film.HfO
2The atomic force microscope of film (AFM) photo (as shown in Figure 3).The surface undulation of film is less, and the roughness RMS (root of mean square) of film is 1.100nm in 2 * 2 mu m ranges.
2. the composition of film.Fig. 4 is the x-ray photoelectron power spectrum (XPS) of hafnia film.Two typical Hf4f peak: Hf4f appear in the XPS curve of film
5/2And Hf4f
7/2Binding energy be respectively 18.55eV and 17.20eV, show HfO
2Film successfully deposits.The binding energy of the 01s of film is measured as 531.85eV, and this value is the binding energy of 01s rump electron in the hafnium silicate.It among Fig. 4 c the common information of silicon substrate Si-Si (98.75eV) and boundary layer Hf-Si-O (102.5eV).
3. the electric property of film.Fig. 5 is HfO
2The C-V of film and J-V curve, the equivalent thickness of visible film is very little, has only 0.84nm, its leakage current density J
AWhen+1V is 0.21A/cm
2
Embodiment 2:
(1) HfCl
4The preparation of colloidal sol:
In the hand behaviour case of nitrogen atmosphere, get the anhydrous HfCl of 0.005mol
4Powder dissolves in the 20ml absolute ethyl alcohol, stirs it is dissolved fully; 3ml acetylacetone,2,4-pentanedione and 17ml absolute ethyl alcohol are mixed, then above two kinds of solution are mixed; Take out the solution for preparing then from hand behaviour case, at room temperature magnetic agitation is 4～7 hours, obtains concentration and is about 0.125mol/l and stable HfCl
4Colloidal sol;
(2) Si substrate processing:
After the cleaning of monocrystalline substrate usefulness standard RCA semiconductor cleaning, at room temperature soak the oxide skin(coating) (volume ratio of hydrofluoric acid and deionized water is 1:10) of removing the surface in 3～6 minutes with diluent hydrofluoric acid solution again; Then this substrate is put into 50 ℃ 30% weight ratio hydrogen peroxide sonicated 8～15 minutes;
(3) thin film preparation process:
At ambient temperature, above-mentioned Si substrate is immersed the HfCl for preparing
4Kept in the colloidal sol 3～5 minutes, and made it saturated absorption; Take out the Si substrate subsequently, and clean the surface with absolute ethyl alcohol; Put into deionized water then and soaked 3～5 minutes, fully hydrolysis generates HfO
2Then dry up sample surfaces with high pure nitrogen; So the above step 8 of circulation time makes HfO
2Film, at last under 800 ℃ in nitrogen atmosphere short annealing made finished product in 5 minutes.
The composition of the above-mentioned finished product that makes and performance parameter:
1. the surface roughness of film.HfO
2The atomic force microscope of film (AFM) photo (as shown in Figure 6).The surface undulation of film is less, and the roughness RMS (root of mean square) of film is 1.111nm in 2 * 2 mu m ranges.
2. the composition of film.Fig. 7 is the x-ray photoelectron power spectrum (XPS) of hafnia film.Two typical Hf4f peak: Hf4f appear in the XPS curve of film
5/2And Hf4f
7/2Binding energy be respectively 18.95eV and 17.55eV, show HfO
2Film successfully deposits.The binding energy of the 01s of film is measured as 532.25eV, and this value is the binding energy of 01s rump electron in the hafnium silicate.It among Fig. 7 c the common information of silicon substrate Si-Si (98.80eV) and boundary layer Hf-Si-O (103.0eV).
3. the electric property of film.Fig. 8 is HfO
2The C-V of film and J-V curve, the equivalent thickness of film are 0.97nm, its leakage current density J
AWhen-1V is 0.4A/cm
2
Embodiment 3:
(1) HfCl
4The preparation of colloidal sol:
In the hand behaviour case of nitrogen atmosphere, get the anhydrous HfCl of 0.02mol
4Powder dissolves in the 40ml absolute ethyl alcohol, stirs it is dissolved fully; 6ml acetylacetone,2,4-pentanedione and 20ml absolute ethyl alcohol are mixed, then above two kinds of solution are mixed; Take out the solution for preparing then from hand behaviour case, at room temperature magnetic agitation is 4～7 hours, obtains concentration and is about 0.3mol/l and stable HfCl
4Colloidal sol;
(2) Si substrate processing:
After the cleaning of monocrystalline substrate usefulness standard RCA semiconductor cleaning, at room temperature soak the oxide skin(coating) (volume ratio of hydrofluoric acid and deionized water is 1:8) of removing the surface in 3～6 minutes with diluent hydrofluoric acid solution again; Then this substrate is put into 30% (mass fraction) hydrogen peroxide sonicated 8～15 minutes of 50 ℃;
(3) thin film preparation process:
At ambient temperature, above-mentioned Si substrate is immersed the HfCl for preparing
4Kept in the colloidal sol 3～5 minutes, and made it saturated absorption; Take out the Si substrate subsequently, and clean the surface with absolute ethyl alcohol; Put into deionized water then and soaked 3～5 minutes, fully hydrolysis generates HfO
2Then dry up sample surfaces with high pure nitrogen; So the above step 35 of circulation time makes HfO
2Film, at last under 800 ℃ in nitrogen atmosphere short annealing made finished product in 3 minutes.
The above-mentioned finished product that makes, the composition of its film and example 1 and 2 similar, and its electric property is as shown in Figure 9, is HfO
2The C-V of film and J-V curve, the equivalent thickness of film are 2.22nm, its leakage current density J
AWhen+1V is 0.07A/cm
2
Embodiment 1:
(1) ZrCl
4The preparation of colloidal sol:
In the hand behaviour case of nitrogen atmosphere, get the anhydrous ZrCl of 0.01mol
4Powder dissolves in the 30ml absolute ethyl alcohol, stirs it is dissolved fully; 5ml acetylacetone,2,4-pentanedione and 15ml absolute ethyl alcohol are mixed, then above two kinds of solution are mixed; Take out the solution for preparing then from hand behaviour case, at room temperature magnetic agitation is 4～7 hours, obtains concentration and is about 0.2mol/l and stable ZrCl
4Colloidal sol;
(2) Si substrate processing:
After the cleaning of monocrystalline substrate usefulness standard RCA semiconductor cleaning, at room temperature soak the oxide skin(coating) (volume ratio of hydrofluoric acid and deionized water is 1: 8) of removing the surface in 3～6 minutes with diluent hydrofluoric acid solution again; Then this substrate is put into 30% (mass fraction) hydrogen peroxide sonicated 8～15 minutes of 60 ℃;
(3) thin film preparation process:
At ambient temperature, above-mentioned Si substrate is immersed the ZrCl for preparing
4Kept in the colloidal sol 3～5 minutes, and made it saturated absorption; Take out the Si substrate subsequently, and clean the surface with absolute ethyl alcohol; Put into deionized water then and soaked 3～5 minutes, fully hydrolysis generates ZrO
2Then dry up sample surfaces with high pure nitrogen; So the above step 30 of circulation time makes ZrO
2Film, at last under 500 ℃ in nitrogen atmosphere short annealing made finished product in 5 minutes.
The composition of the above-mentioned finished product that makes and performance parameter:
Figure 10 is the x-ray photoelectron power spectrum (XPS) of zirconia film, and binding energy is 185.25eV and the corresponding ZrO of 182.90eV difference
2Middle Zr3d
3/2And Zr3d
5/2The photoelectron characteristic peak.Figure 10 (b) is a 01s photoelectron binding energy (532.05eV), corresponding ZrO
2The middle pairing binding energy of 01s.It among Figure 10 c the common information of silicon substrate Si-Si (98.9eV) and boundary layer Zr-Si-O (102.8eV).These results show ZrO
2Film successfully deposits.
Embodiment 2:
(1) ZrCl
4The preparation of colloidal sol:
In the hand behaviour case of nitrogen atmosphere, get the anhydrous ZrCl of 0.005mol
4Powder dissolves in the 20ml absolute ethyl alcohol, stirs it is dissolved fully; 3ml acetylacetone,2,4-pentanedione and 17ml absolute ethyl alcohol are mixed, then above two kinds of solution are mixed; Take out the solution for preparing then from hand behaviour case, at room temperature magnetic agitation is 4～7 hours, obtains concentration and is about 0.125mol/l and stable ZrCl
4Colloidal sol;
(2) Si substrate processing:
After the cleaning of monocrystalline substrate usefulness standard RCA semiconductor cleaning, at room temperature soak the oxide skin(coating) (volume ratio of hydrofluoric acid and deionized water is 1:10) of removing the surface in 3～6 minutes with diluent hydrofluoric acid solution again; Then this substrate is put into 50 ℃ 30% weight ratio hydrogen peroxide sonicated 8～15 minutes;
(3) thin film preparation process:
At ambient temperature, above-mentioned Si substrate is immersed the ZrCl for preparing
4Kept in the colloidal sol 3～5 minutes, and made it saturated absorption; Take out the Si substrate subsequently, and clean the surface with absolute ethyl alcohol; Put into deionized water then and soaked 3～5 minutes, fully hydrolysis generates ZrO
2Then dry up sample surfaces with high pure nitrogen; So the above step 8 of circulation time makes ZrO
2Film, at last under 800 ℃ in nitrogen atmosphere short annealing made finished product in 3 minutes.
Embodiment 3:
(1) ZrCl
4The preparation of colloidal sol:
In the hand behaviour case of nitrogen atmosphere, get the anhydrous ZrCl of 0.02mol
4Powder dissolves in the 40ml absolute ethyl alcohol, stirs it is dissolved fully; 6ml acetylacetone,2,4-pentanedione and 20ml absolute ethyl alcohol are mixed, then above two kinds of solution are mixed; Take out the solution for preparing then from hand behaviour case, at room temperature magnetic agitation is 4～7 hours, obtains concentration and is about 0.3mol/l and stable ZrCl
4Colloidal sol;
(2) Si substrate processing:
After the cleaning of monocrystalline substrate usefulness standard RCA semiconductor cleaning, at room temperature soak the oxide skin(coating) (volume ratio of hydrofluoric acid and deionized water is 1:8) of removing the surface in 3～6 minutes with diluent hydrofluoric acid solution again; Then this substrate is put into 30% (mass fraction) hydrogen peroxide sonicated 8～15 minutes of 50 ℃;
(3) thin film preparation process:
At ambient temperature, above-mentioned Si substrate is immersed the ZrCl for preparing
4Kept in the colloidal sol 3～5 minutes, and made it saturated absorption; Take out the Si substrate subsequently, and clean the surface with absolute ethyl alcohol; Put into deionized water then and soaked 3～5 minutes, fully hydrolysis generates ZrO
2Then dry up sample surfaces with high pure nitrogen; So the above step 50 of circulation time makes ZrO
2Film, at last under 500 ℃ in nitrogen atmosphere short annealing made finished product in 5 minutes.
Claims (2)
1, the ultra-thin HfO of a kind of preparation
2Or ZrO
2The soft chemical method of gate dielectric membrane is characterized in that may further comprise the steps:
(1) HfCl
4Or ZrCl
4The preparation of colloidal sol:
In the hand behaviour case of nitrogen atmosphere, get the anhydrous HfCl of 0.005～0.02mol
4Or anhydrous ZrCl
4Powder dissolves in 20～40ml absolute ethyl alcohol, stirs it is dissolved fully; 3～6ml acetylacetone,2,4-pentanedione and 10～20ml absolute ethyl alcohol are mixed, then above two kinds of solution are mixed; Take out the solution for preparing then from hand behaviour case, at room temperature magnetic agitation is 4～7 hours, and obtaining concentration is 0.1～0.4mol/l and stable HfCl
4Or ZrCl
4Colloidal sol;
(2) Si substrate processing:
After the cleaning of monocrystalline substrate usefulness standard RCA semiconductor cleaning, at room temperature soak the oxide skin(coating) of removing the surface in 3～6 minutes with diluent hydrofluoric acid solution again; Then this substrate is put into 30% (mass fraction) hydrogen peroxide sonicated 8～15 minutes of 50～80 ℃;
(3) thin film preparation process:
At ambient temperature, above-mentioned Si substrate is immersed the HfCl for preparing
4Or ZrCl
4Kept in the colloidal sol 3～5 minutes, and made it saturated absorption; Take out the Si substrate subsequently, and clean the surface with absolute ethyl alcohol; Put into deionized water then and soaked 3～5 minutes, fully hydrolysis generates HfO
2Or ZrO
2Then dry up sample surfaces with high pure nitrogen; So circulation above step 8～50 time make HfO
2Or ZrO
2Film, at last under 400～800 ℃ in nitrogen atmosphere short annealing made finished product in 3～5 minutes.
2, the ultra-thin HfO of preparation according to claim 1
2Or ZrO
2The soft chemical method of gate dielectric membrane is characterized in that in the Si substrate processing process, the volume ratio of hydrofluoric acid and deionized water is 1:8～1:10 in the hydrofluoric acid solution.
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| CN104009093B (en) * | 2014-06-13 | 2016-08-31 | 青岛大学 | A kind of preparation method of high k dielectric layer aqueous indium oxide film transistor |
| CN113539812B (en) * | 2021-07-14 | 2024-04-26 | 湘潭大学 | Method for regulating and controlling electrical properties of hafnium oxide-based ferroelectric film by homogenous seed layer |
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| CN101154588A (en) * | 2006-09-30 | 2008-04-02 | 三星电子株式会社 | Composition for dielectric thin film, metal oxide dielectric thin film using the same and preparation method thereof |
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| CN101154588A (en) * | 2006-09-30 | 2008-04-02 | 三星电子株式会社 | Composition for dielectric thin film, metal oxide dielectric thin film using the same and preparation method thereof |
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Correction item: Denomination of Invention Correct: A soft chemical method for preparing ultra-thin HfO#-[2] or ZrO#-[2] gate dielectric films False: A soft chemical method for preparing ultra-thin HfO#-[2] or ZrO#-[3] gate dielectric films Number: 38 Page: 1810 Volume: 25 |
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Correction item: Denomination of Invention Correct: A soft chemical method for preparing ultra-thin HfO#-[2] or ZrO#-[2] gate dielectric films False: A soft chemical method for preparing ultra-thin HfO#-[2] or ZrO#-[3] gate dielectric films Number: 38 Page: The title page Volume: 25 |
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Free format text: CORRECT: INVENTION NAME; FROM: PREPARING SUPERTHIN HFO#- (2) OR ZRO #- (3) SOFT CHEMISTRY METHOD OFGRATING DIELECTRIC THIN FILM - TO: PREPARING SUPERTHIN HFO#- (2) OR ZRO #- (2) SOFT CHEMISTRY METHOD OF GRATING DIELECTRIC THIN FILM - |
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Granted publication date: 20090923 Termination date: 20120529 |