CN102094190A - Preparation method of lanthanum-based high-dielectric constant film - Google Patents
Preparation method of lanthanum-based high-dielectric constant film Download PDFInfo
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- CN102094190A CN102094190A CN 201010556701 CN201010556701A CN102094190A CN 102094190 A CN102094190 A CN 102094190A CN 201010556701 CN201010556701 CN 201010556701 CN 201010556701 A CN201010556701 A CN 201010556701A CN 102094190 A CN102094190 A CN 102094190A
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Abstract
The invention belongs to the technical field of a semiconductor integrated circuit, and specifically relates to a lanthanum-based high-dielectric constant film material and a preparation method thereof. By adopting an atomic layer deposition process and using oxydol as an oxidation reaction precursor required for the atomic layer deposition process, the invention effectively overcomes the defect that the reaction is difficult to perform as a result of the low oxidation ability of water used as the oxidation reaction precursor. By using the method, a high-quality lanthanum-based high-dielectric constant film can be prepared, and the characteristics of the film can be easily optimized by the hybrid film growth technology, thereby overcoming the thermal stability and water absorption defects of a pure binary lanthanum oxide film.
Description
Technical field
The invention belongs to the semiconductor integrated circuit technical field, be specifically related to a kind of preparation method of lanthanum base high dielectric constant film.
Background technology
Along with constantly dwindling of metal-oxide semiconductor fieldeffect transistor (MOSFETs) characteristic dimension, the insulated gate medium layer also thins down according to the principle of scaled down, after gate dielectric layer is thinned to a certain degree, its integrity problem, especially with the puncture of time correlation and the impurity in the gate electrode to the problems such as diffusion of substrate, will have a strong impact on performance, stability and the reliability of device.Now, in the CMOS integrated circuit technology, extensively adopt high-k (high k) gate medium to replace SiO
2As gate dielectric material, thereby can effectively reduce gate leakage current at the physical thickness that keeps increasing under the constant condition of equivalent oxide thickness (EOT) gate dielectric layer.
At present, in the technology of preparation high dielectric constant material film, atomic layer deposition (ALD) is to generally acknowledge the most excellent preparation method.Atomic layer deposition is a kind of through utilizing surperficial saturated reaction on the substrate of surface-active-treatment, and to temperature and the not too responsive deposition process of reactant flux, the flow process that adopts atomic layer deposition prepared film as shown in Figure 1.In the atomic layer deposition process, the chemical reaction of new one deck atomic film is directly to be associated with preceding one deck, and this mode makes each reaction deposit one deck atom, just can precisely control the thickness of film by the quantity that controls reaction time.For traditional depositing technics, the atomic layer deposition method all has remarkable advantages at the aspects such as homogeneity, step coverage rate and gauge control of film.
Lanthanum trioxide (La
2O
3) as a kind of alternative high-k gate dielectric material, it has advantages such as high specific inductivity (relative permittivity is about 30), stable chemical property and enough being with differ from.But, adopt water as the atomic layer deposition oxidizing reaction precursor La that grows
2O
3Be difficult for carrying out, seek the key that suitable atomic layer deposition reactions precursor and the suitable atomic layer deposition technology of design become the high-quality lanthanum base high dielectric constant film of preparation.
Summary of the invention
The objective of the invention is to propose a kind of suitable atomic layer deposition reactions precursor and suitable atomic layer deposition technology of adopting, preparation lanthanum base high dielectric constant film method is to obtain high-quality lanthanum base high dielectric constant film.
The preparation method of the lanthanum base high dielectric constant film that the present invention proposes is to adopt the method for hydrogen peroxide as the atomic layer deposition lanthanum trioxide film of oxidizing reaction precursor, and concrete steps are:
With the atomic layer deposition reactions chamber of packing into of the semiconducter substrate after cleaning;
Temperature in the atomic layer deposition reactions chamber is risen to 300-450 ℃;
Pressure in the atomic layer deposition reactions chamber is risen to 0.5-5torr;
Carry out the atomic layer deposition lanthanum trioxide thin-film technique in a plurality of cycles, form the lanthanum trioxide film of desired thickness.
Further, described semiconducter substrate is Si, Ge, Ge
xSi
1-x, semiconductor material such as GaAs.The one-period of described atomic layer deposition lanthanum trioxide thin-film technique comprises:
To heat solid state reaction precursor La (thd)
3The gas that volatilizes is introduced the atomic layer deposition reactions chamber with impulse form, and the burst length is 2-10 second;
Non-active gas is introduced the atomic layer deposition reactions chamber with impulse form, remove unreacted metal organic precursor and by product in the atomic layer deposition reactions chamber, the burst length is 2-30 second;
The hydrogen peroxide steam is introduced the atomic layer deposition reactions chamber with impulse form, and the burst length is 2-10 second;
Non-active gas is introduced the atomic layer deposition reactions chamber with impulse form, remove unreacted hydrogen peroxide steam and by product in the atomic layer deposition reactions chamber, the burst length is 2-30 second.
Further, described non-active gas is nitrogen, argon gas or is helium.
The pure zirconia lanthanum has shortcomings such as poor heat stability, easy water-absorbent, can not satisfy the user demand of unicircuit gate medium, therefore the invention allows for a kind of method of preparation of lanthanum base high-k mixed film, realize based on the optimization of lanthanum base gate dielectric membrane Devices Characteristics, the method of the preparation of described lanthanum base high-k mixed film, be exactly after above-mentioned atomic layer deposition forms the lanthanum trioxide film, proceed the atomic layer deposition high dielectric constant material thin-film technique in a plurality of cycles, form the high dielectric constant material film of desired thickness.Be exactly specifically:
With the atomic layer deposition reactions chamber of packing into of the semiconducter substrate after cleaning;
It is temperature required that the atomic layer deposition reactions chamber is heated to technology;
The atomic layer deposition reactions chamber is risen to the required pressure of technology;
Carry out the atomic layer deposition lanthanum trioxide thin-film technique in a plurality of cycles, form the lanthanum trioxide film of desired thickness;
(processing condition of above-mentioned steps are the same)
Then, proceed the atomic layer deposition high dielectric constant material thin-film technique in a plurality of cycles, form the high dielectric constant material film of desired thickness.
Here, described atomic layer deposition high dielectric constant material thin-film technique of carrying out a plurality of cycles, its step and condition are identical with the atomic layer deposition lanthanum trioxide thin-film technique of carrying out a plurality of cycles.But, the solid state reaction precursor here is the precursor of described high dielectric constant material.
Further, described high dielectric constant material is Ta
2O
5, Pr
2O
3, TiO
2, HfO
2, Al
2O
3Or ZrO
2Contour k gate dielectric material.Its reaction precursor body is respectively: Ta (OEt)
5, Pr (tmhd)
3, TiCl
4, Hf (OEt)
4, Al (CH)
3, Zr (thd)
4
The present invention adopts atomic layer deposition technology, with hydrogen peroxide as the required oxidizing reaction precursor of atomic layer deposition technology, effectively overcome traditional with water as oxidizing reaction precursor oxidation capacity a little less than and cause reacting and be difficult for the defective of carrying out, can prepare high-quality lanthanum base high dielectric constant film, and be easy to adopt the mixed film growing technology to optimize the adjusting film characteristics, thereby overcome the deficiency of pure binary lanthanum trioxide film on thermostability and easy water-absorbent.
Description of drawings
Fig. 1 prepares the schema of film for adopting the atomic layer deposition technology.
The lanthanum trioxide membrane structure of Fig. 2 for adopting the technology of the present invention on substrate, to prepare.
The lanthanum base mixed film structure of Fig. 3 for adopting the technology of the present invention on substrate, to prepare.
Fig. 4 is the Al based on the atomic layer deposition prepared
2O
3/ La
2O
3The C-V rational curve of gate medium.
Fig. 5-Fig. 7 is preparation technology's schema of the embodiment of the lanthanum base resistance-change memory device of the 1T-1R structure of employing the technology of the present invention.
Embodiment
Below with reference to accompanying drawings illustrative embodiments of the present invention is elaborated.In the drawings, for convenience of description, amplify or dwindled the thickness in layer and zone, shown in size do not represent physical size.Although the physical size that reflects device that these figure can not entirely accurate, their zones that still has been complete reflection and form mutual alignment between the structure, particularly form between the structure up and down and neighbouring relations.
When adopting atomic layer deposition technology growth oxidation lanthanum film, at first, the substrate material 201 after cleaning is put into the atomic layer deposition reactions chamber, substrate material is such as selecting silicon materials.Then the temperature in the atomic layer deposition reactions chamber is risen to 300 ℃, pressure and rise to about 1torr, and in whole atomic layer deposition technology, keep this temperature and pressure.
Next, with La (thd)
3As the precursor of lanthanum (La), hydrogen peroxide (H
2O
2) as the precursor of oxygen (O), carry out the atomic layer deposition lanthanum trioxide technology in 2-5 cycle on the surface of silicon substrate 201, form lanthanum trioxide film 202, as shown in Figure 2.
When forming lanthanum trioxide film 202, the one-period of atomic layer deposition lanthanum trioxide thin-film technique comprises:
1. will heat solid state reaction precursor La (thd)
3The gas that volatilizes is incorporated in the atomic layer deposition reactions chamber with impulse form, and the burst length is 2 seconds.
2. helium is introduced the atomic layer deposition reactions chamber with impulse form, remove unreacted metal organic precursor and by product in the atomic layer deposition reactions chamber, the burst length is 5 seconds.
3. the hydrogen peroxide steam is incorporated in the atomic layer deposition reactions chamber with pulse, the burst length is 2 seconds.
4. helium is introduced the atomic layer deposition reactions chamber with impulse form, remove unreacted hydrogen peroxide steam and by product in the atomic layer deposition reactions chamber, the burst length is 5 seconds.
By the cycle life of control atomic layer deposition lanthanum trioxide technology, the accurately thickness of controlled oxidation lanthanum film.
For realizing optimizing based on lanthanum base gate medium Devices Characteristics, and overcome pure binary lanthanum trioxide film in thermostability and the easy deficiency on the water-absorbent, can also adopt the atomic layer deposition technology to come the adjustable lanthanum base mixed film of processability, such as, behind lanthanum trioxide film 202 growth endings, continue to adopt atomic layer deposition technology one deck aluminium sesquioxide (Al that on lanthanum trioxide film 202, grows
2O
3) film 203, as shown in Figure 3.Wherein, the one-period of atomic layer deposition aluminium sesquioxide film comprises:
1. will heat liquid reaction precursor trimethyl aluminium (Al (CH
3)
3) gas that volatilizes is incorporated in the atomic layer deposition reactions chamber with impulse form, the burst length is 2 seconds.
2. helium is introduced the atomic layer deposition reactions chamber with impulse form, remove unreacted metal organic precursor and by product in the atomic layer deposition reactions chamber, the burst length is 3 seconds.
3. the hydrogen peroxide steam is incorporated in the atomic layer deposition reactions chamber with pulse, the burst length is 2 seconds.
4. helium is introduced the atomic layer deposition reactions chamber with impulse form, remove unreacted hydrogen peroxide steam and by product in the atomic layer deposition reactions chamber, the burst length is 3 seconds.
Can accurately control the thickness of aluminium sesquioxide film by the cycle life of regulating atomic layer deposition aluminium sesquioxide thin-film technique.
After forming aluminium sesquioxide film 203, sample is carried out so utilizing photoetching, evaporation technology to form electrode pattern after rta technique handles, in the MOS structure that forms, can obtain excellent C-V rational curve, as shown in Figure 4.
The preparation method of lanthanum base mixed film proposed by the invention can be widely used in high-k gate dielectric/La
2O
3In the MOS device of stack architecture, employing the technology of the present invention of the following stated prepares the technological process of the embodiment of the adjustable lanthanum base resistance-change memory device of the performance of 1T-1R structure.
At first, lanthanum base mixed film structure as shown in Figure 3 with the preparation of employing the technology of the present invention is substrate, in conjunction with the CMOS silicon technology, the certain metal of deposit on aluminium sesquioxide film 203 at first, such as being adulterated polysilicon membrane 204, mask, exposure etching form the grid structure of device then, form the source region 205 and the drain region 206 of device again by ion implantation technology, thereby form the MOSFET structure, as shown in Figure 5.
Next, deposit forms sealing coat 207 and mask layer 208 successively, and sealing coat 207 is such as being silicon-dioxide, and mask layer 208 is selected silicon nitride.Then mask, exposure, etching form contact hole, adopt deposition process such as physical vapor deposition (PVD) or chemical vapor deposition (CVD) to prepare one deck diffusion impervious layer 209 then, diffusion impervious layer 209 is preferably the Ti/TiN composite bed, the deposition tungsten metal level 210 then, and by chemically machinery polished (CMP) method formed structure planarization formed the tungsten plug structure.
After the tungsten plug structure forms, continue deposit one layer insulating 211, insulation layer 211 is such as being silicon-dioxide, and mask, exposure, etching form through hole then.Adopt deposition process such as physical vapor deposition (PVD) or chemical vapor deposition (CVD) to prepare diffusion impervious layer 212 then, diffusion impervious layer 212 is selected the Ti/TiN composite bed.Utilize metals such as electron beam evaporation, physical vapour deposition prepared Pt such as (PVD), Pd, Au, Al as resistance-change memory device bottom electrode 213, as shown in Figure 6 again.
At last, deposit one layer insulating 214, insulation layer 214 is such as being silicon nitride, mask, exposure, etching form through hole then, utilize atomic layer deposition technology to form the adjustable lanthanum base resistive thin film layer 215 of performance again, adopt electron beam evaporation, physical vapour deposition prepared TiN such as (PVD), metals such as Au, Al upper current conducting cap 216 then, and then finish the preparation of the resistance-change memory device of 1T-1R structure, as shown in Figure 7 as the resistance-change memory device.
As mentioned above, under the situation that does not depart from spirit and scope of the invention, can also constitute many very embodiment of big difference that have.Should be appreciated that except as defined by the appended claims, the invention is not restricted at the specific examples described in the specification sheets.
Claims (6)
1. the preparation method of a lanthanum trioxide film is characterized in that concrete steps are:
With the atomic layer deposition reactions chamber of packing into of the semiconducter substrate after cleaning;
The atomic layer deposition reactions chamber is heated to the temperature required 300-450 of technology ℃;
The atomic layer deposition reactions chamber is risen to the required pressure 0.5-5torr of technology;
Carry out the atomic layer deposition lanthanum trioxide thin-film technique in a plurality of cycles, form the lanthanum trioxide film of desired thickness.
2. preparation method according to claim 1 is characterized in that, described semiconducter substrate is Si, Ge, Ge
xSi
1-xOr GaAs.
3. the preparation method of lanthanum trioxide film according to claim 1 is characterized in that, the one-period of described atomic layer deposition lanthanum trioxide thin-film technique comprises:
To heat solid state reaction precursor La (thd)
3The gas that volatilizes is introduced the atomic layer deposition reactions chamber with impulse form; Described evaporable La (thd)
3The burst length of gas is 2-10 second;
Non-active gas is introduced the atomic layer deposition reactions chamber with impulse form, remove unreacted metal organic precursor and by product in the atomic layer deposition reactions chamber; The burst length of described twice non-active gas is 2-30 second;
The hydrogen peroxide steam is introduced the atomic layer deposition reactions chamber with impulse form; The burst length of described hydrogen peroxide steam is 2-10 second;
Non-active gas is introduced the atomic layer deposition reactions chamber with impulse form, remove unreacted hydrogen peroxide steam and by product in the atomic layer deposition reactions chamber; The burst length of described twice non-active gas is 2-30 second.
4. preparation method according to claim 3 is characterized in that, described non-active gas is nitrogen, argon gas or helium.
5. the preparation method of a lanthanum base high-k mixed film is characterized in that concrete steps are:
Adopt as one of claim 1-4 as described in the preparation method, the lanthanum trioxide film of formation desired thickness;
Then, proceed the atomic layer deposition high dielectric constant material thin-film technique in a plurality of cycles, form the high dielectric constant material film of desired thickness.
6. the preparation method of lanthanum base high-k mixed film according to claim 5 is characterized in that described high dielectric constant material is Ta
2O
5, Pr
2O
3, HfO
2, Al
2O
3Or ZrO
2
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|---|---|---|---|
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20030072882A1 (en) * | 2001-08-03 | 2003-04-17 | Jaakko Niinisto | Method of depositing rare earth oxide thin films |
| CN1560905A (en) * | 2004-02-16 | 2005-01-05 | 南京大学 | Method for preparing stabilizing rare-earth oxide grate dielectric film |
| US20050051828A1 (en) * | 2003-04-22 | 2005-03-10 | Park Ki-Yeon | Methods of forming metal thin films, lanthanum oxide films, and high dielectric films for semiconductor devices using atomic layer deposition |
-
2010
- 2010-11-24 CN CN 201010556701 patent/CN102094190A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20030072882A1 (en) * | 2001-08-03 | 2003-04-17 | Jaakko Niinisto | Method of depositing rare earth oxide thin films |
| US20050051828A1 (en) * | 2003-04-22 | 2005-03-10 | Park Ki-Yeon | Methods of forming metal thin films, lanthanum oxide films, and high dielectric films for semiconductor devices using atomic layer deposition |
| CN1560905A (en) * | 2004-02-16 | 2005-01-05 | 南京大学 | Method for preparing stabilizing rare-earth oxide grate dielectric film |
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Application publication date: 20110615 |