CN109338331A - A kind of preparation method and its product of the zirconia film of the silicon doping of high dielectric constant - Google Patents

A kind of preparation method and its product of the zirconia film of the silicon doping of high dielectric constant Download PDF

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CN109338331A
CN109338331A CN201811420812.6A CN201811420812A CN109338331A CN 109338331 A CN109338331 A CN 109338331A CN 201811420812 A CN201811420812 A CN 201811420812A CN 109338331 A CN109338331 A CN 109338331A
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Hefei Anderkeming Semiconductor Technology Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
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    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
    • C23C16/455—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating characterised by the method used for introducing gases into reaction chamber or for modifying gas flows in reaction chamber
    • C23C16/45523—Pulsed gas flow or change of composition over time
    • C23C16/45525—Atomic layer deposition [ALD]
    • C23C16/45553—Atomic layer deposition [ALD] characterized by the use of precursors specially adapted for ALD
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
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    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
    • C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
    • C23C16/455—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating characterised by the method used for introducing gases into reaction chamber or for modifying gas flows in reaction chamber
    • C23C16/45523—Pulsed gas flow or change of composition over time
    • C23C16/45525—Atomic layer deposition [ALD]
    • C23C16/45527—Atomic layer deposition [ALD] characterized by the ALD cycle, e.g. different flows or temperatures during half-reactions, unusual pulsing sequence, use of precursor mixtures or auxiliary reactants or activations
    • C23C16/45536—Use of plasma, radiation or electromagnetic fields
    • C23C16/4554—Plasma being used non-continuously in between ALD reactions

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Abstract

The present invention provides the preparation method and its product of a kind of zirconia film of good, the uniform high dielectric constant of Elemental redistribution the silicon doping of thermal stability, using (Me3SiCp)Zr(NMe2)3As at least one presoma, deposited by way of thermal atomic layer deposition method or plasma enhanced atomic layer deposition method；Wherein Cp represents cyclopentadienyl group, and Me is methyl.The present invention uses (Me3SiCp)Zr(NMe2)3As the main component of presoma, without adding Si further according to ratio, without using ZrO again2/SiO2Silicon is doped on zirconia film by the mode of alternating deposit, be can be realized in film being uniformly distributed for different elements, is also greatly simplified production process；And cyclopentadienyl group (Cp) is ring structure, stable structure can be improved the thermal stability of molecule, and then improve the thermal stability of deposition film, it is not easy to generate crystal boundary leakage current.

Description

A kind of preparation method and its product of the zirconia film of the silicon doping of high dielectric constant
Technical field
The present invention relates to technical field of semiconductors, are especially a kind of zirconia film of the silicon doping of high dielectric constant Preparation method and its product.
Background technique
In the semiconductor industry, memory and logical device are its most important component parts, and dielectric material this two Belong to core again in kind device, therefore, to a certain extent, the further development of semiconductor depends on further dashing forward for dielectric material It is broken.Such as: in dynamic RAM (DRAM), the amount of storage of DRAM depends on the quantity of capacitor；Increasing capacitor quantity While, the capacitance of each capacitor can reduce because of the reduction of area；It is original in order to meet the requirement of position of minimum capacitance Dielectric material (SiO2, SiN etc.) must be replaced by new high dielectric constant material (i.e. high-k), in the same of minification When reach the requirement of position of minimum capacitance, realization avoids loss power, increases the service life, improves capacity, accelerates the purpose of storage speed. For another example: in high definition display technology (by taking high definition mobile phone display screen as an example), each pixel (luminous point) of display screen can be equipped with One or more capacitors；The maximum brightness that the capacitance (ability of storage electronics) of capacitor determines each pixel, improves pixel Brightness help to improve mobile phone show content readability；While improving mobile phone pixel, capacity area can be because of area Reduction and reduce；For the purposes of meeting the requirement of capacitance, original dielectric constant will also be replaced by high dielectric constant material, This is also the only way which must be passed of the following high-resolution display technology.
In the prior art, silica, silicon nitride, aluminium oxide, zirconium oxide, hafnium oxide etc. are generallyd use and is used as dielectric material Material forms thin film capacitor.In these dielectric substances, zirconium oxide (ZrO2) there is high dielectric constant, and on 250 DEG C of left sides It can form a film in a low temperature of the right side, be very suitable to form the thin film capacitor of small size, bulky capacitor, solve dynamic at present so becoming Store one of (DRAM) and the optimal material selection of high definition display technology problem.But zirconium oxide (ZrO2) film be easy to compared with Crystal structure is formed under low temperature or in lower temperature heating process, once zirconium oxide (ZrO2) film crystallizes, it will The roughness of film surface is caused to increase, in electrode layer and zirconium oxide (ZrO2) film grain boundaries (the i.e. big ZrO of surface roughness2 The surface of film) it is easy for generating higher leakage current density, leakage current becomes larger when capacitor being caused to function, final sensor Failure.Therefore, zirconium oxide (ZrO2) film growth quality it is extremely important for forming reliable high dielectric layer.
Zirconium oxide (ZrO2) film quality depend on its preparation process.Currently, PEALD (plasma enhanced atomic layer Deposition, Plasma EnhancedAtomic Layer Deposition) it is high dielectric constant zirconium oxide (ZrO2) film it is excellent The preparation method of choosing, related technical personnel commonly use four (methylethylamino) zirconium (Zr (NEtMe)4, abbreviation TEMAZ) and raw as PEALD Long ZrO2Presoma.But TEMAZ has the shortcomings that some inherent, its thermal stability is not high enough first, thus limits The temperature of film deposition, causes the film equality not high enough；And wherein the impurity contents such as N, C are high, so that film crystal unity Excessively high (i.e. surface roughness is high), reduces the dielectric constant of final film in this way, leads to zirconium oxide (ZrO2) film quality It is not high.
To solve drawbacks described above, related technical personnel use the zirconium oxide (ZrO of silicon (Si) doping2) film substitution pure zirconia Zirconium (ZrO2) film, such film crystallization temperature is than pure ZrO2High (> 700 DEG C), keep under lower temperature (700 DEG C or less) Preferable noncrystalline structure, effectively reduces crystal boundary leakage current.But how to prepare the zirconium oxide of silicon (Si) Uniform Doped (ZrO2) film, and become new problem.Currently, zirconium oxide (the ZrO of silicon (Si) doping2) film is using ZrO2/SiO2It hands over For the growth pattern of deposition, but to frequently result in Elemental redistribution uneven for this mode, and two presomas interactions flow into reaction In chamber, so that process and equipment are all extremely complex, become difficult presoma in the chemisorption on surface.So how Prepare the zirconium oxide (ZrO of silicon (Si) doping of high quality2) film, it is further to break through high dielectric constant material at present and then push away The problem for needing to overcome of dynamic semiconductor device development.
Summary of the invention
Uniformly high dielectric is normal for a kind of the technical problem to be solved by the invention is to provide thermal stability good, Elemental redistribution The preparation method and its product of the zirconia film of several silicon doping.
Technical solution of the invention is as follows:
A kind of preparation method of the zirconia film of the silicon doping of high dielectric constant, which is characterized in that use (Me3SiCp) Zr(NMe2)3As at least one presoma, pass through thermal atomic layer deposition method or plasma enhanced atomic layer deposition method Mode deposits；Wherein Cp represents cyclopentadienyl group, and Me is methyl.
The present invention uses (Me3SiCp)Zr(NMe2)3(three (dimethylamino)-trimethyl silicon substrates-cyclopentadienyl group zirconium) are made For the main component of presoma, two kinds of elements of Si and Zr are provided simultaneously with, and the ratio of Si and Zr is 1:1 in compound, thus Without adding Si further according to ratio, without using ZrO again2/SiO2Silicon is doped to zirconia film by the mode of alternating deposit On, so being fully able to realize being uniformly distributed for different elements in film, also greatly simplify production process；And cyclopentadienyl group It (Cp) is ring structure, stable structure so can be improved the thermal stability of molecule, and then improves the thermostabilization of deposition film Property, good amorphous phase is still able to maintain until 800 DEG C, it is not easy to generate crystal boundary leakage current, improve high dielectric constant significantly The growth quality of film.
Preferably, only with (Me3SiCp)Zr(NMe2)3Unique a kind of presoma as element silicon and zr element source.
Preferably, the described (Me3SiCp)Zr(NMe2)3Synthetic method the following steps are included:
1) by tetramethyl acylamino- zirconium (Zr (NMe2)4) be dissolved in n-hexane, obtain solution A；
2) by Trimethylsilylcyclopendiene (Me3SiCpH, wherein Cp is cyclopentadienyl group-C5H5) it is dissolved in n-hexane In, obtain B solution；
3) B solution is slowly dropped into solution A at -5~5 DEG C, is continuously stirred at room temperature；
4) it is evaporated under reduced pressure under conditions of temperature is 100~120 DEG C, pressure is 1.3~4Pa, removes n-hexane, obtained thick Product；
5) crude product is purified by 1~4 vacuum distillation to get (Me3SiCp)Zr(NMe2)3。
It is further preferred that the ratio between amount of substance of tetramethyl acylamino- zirconium and Trimethylsilylcyclopendiene is 1: (0.8 ~1.0).Tetramethyl acylamino- zirconium is slightly excessive, to guarantee that fully reacting carries out.
Preferably, there are two types of above-mentioned deposition methods, the first uses thermal atomic layer deposition method (ThermalALD), and second Kind using plasma enhancing Atomic layer deposition method (PEALD).
The thermal atomic layer deposition method the following steps are included:
1) by presoma (Me3SiCp)Zr(NMe2)3It is heated to 60~80 DEG C, and with the inertia comprising argon gas or nitrogen Gas is as delivery gas, by (Me3SiCp)Zr(NMe2)3It is input in atomic layer deposition reaction chamber；
2) using the inert gas comprising argon gas or nitrogen as purge gas, excessive presoma is pumped out；
3) make oxidant as main component to ozone or vapor, with the inertia comprising helium, argon gas or nitrogen Gas as delivery gas, 200~500 DEG C at a temperature of reacted；
4) reaction is repeated the above steps until obtaining the film of required thickness.
It is further preferred that the boot speed of above-mentioned oxidant is 50~500sccm.
The plasma enhanced atomic layer deposition method the following steps are included:
1) by presoma (Me3SiCp)Zr(NMe2)360~80 DEG C are heated to, with including the lazy of helium, argon gas or nitrogen Property gas, by (Me3SiCp)Zr(NMe2)3It is input in atomic layer deposition reaction chamber, is allowed to be adsorbed on substrate surface；
2) using the inert gas comprising helium, argon gas or nitrogen as purge gas, excessive presoma is pumped out；
3) source gas to oxygen, nitrous oxide or carbon dioxide gas as main component as plasma Body, use the inert gas comprising helium, argon gas or nitrogen as delivery gas, 100~300 DEG C at a temperature of and wait from Sub- gas is reacted in the case where being formed with the presoma of substrate surface；
4) reaction is repeated the above steps until obtaining the film of required thickness.
Preferably, the boot speed of the source gas of the plasma is 50~100sccm.
The present invention also provides a kind of zirconia films of the silicon of high dielectric constant doping, which is characterized in that using as before Preparation method described in text obtains.
Further, surface roughness≤0.5nm of the film.
Beneficial effects of the present invention are as follows:
(1) using the presoma (Me containing elements Si and Zr simultaneously3SiCp)Zr(NMe2)3, can successful deposition obtain In the uniform film of atomic level Elemental redistribution；When growing film, flowed into reaction chamber without using two presoma interactions, So that reaction process is simplified significantly, equipment requirement is reduced, and the self limiting for also optimizing persursor material in substrate surface adsorbs Effect；
(2) presoma (Me is used3SiCp)Zr(NMe2)3As film deposition precursor body, film heat stability is good, film The temperature range of deposition is wide, and growth rate is high, and uniformity of film is good, dielectric constant height (10~15)；
(3) film crystallization temperature is than pure ZrO2Height, without specific crystal ZrO2Peak has preferable amorphous phase, from 100C It is able to maintain good amorphous phase to 700 DEG C, film formation surface roughness is low (≤0.5nm), reduce the generation of crystal boundary leakage current, Greatly improve the growth quality of film；
(4) presoma (Me is made with the method for the invention3SiCp)Zr(NMe2)3Yield is high, and by-product is few, is easy to mention Pure, the thermostabilization of product is good, is suitable for the presoma of atomic layer deposition；And raw material tetramethyl acylamino- when precursor preparation The ratio of zirconium and Trimethylsilylcyclopendiene does not require too strictly obtain the compound that Si and Zr ratio is 1:1, this Without adding Si further according to ratio when sample prepares film, without using ZrO again2/SiO2The mode deposition of elements Si of alternating deposit And Zr, realize that Elemental redistribution is uniform, simplification of flowsheet.
Detailed description of the invention
Fig. 1 is the XRD spectrum of film product, wherein (1) is the siliceous zirconia film of thermal atomic layer deposition (ZrSiOx) XRD spectrum；It (2) is the siliceous zirconia film (ZrSiO of plasma enhanced atomic layer depositionx) XRD diagram Spectrum；(3) the siliceous zirconia film (ZrSiO of plasma enhanced atomic layer depositionx) it is annealed to the XRD spectrum after 700 DEG C； (4) the siliceous zirconia film (ZrSiO of plasma enhanced atomic layer depositionx) it is annealed to the XRD spectrum after 750 DEG C.
Fig. 2 is the siliceous zirconia film (ZrSiO of plasma enhanced atomic layer depositionx) XPS spectrum figure, wherein (1) peak 3d for being Zr, (2) are the peak 2p of Si, and (3) are the peak 1s of O.
Fig. 3 is the siliceous zirconia film (ZrSiO of plasma enhanced atomic layer depositionx) AFM figure, can see Out, the element of film is evenly distributed in atomic level.
Specific embodiment
The present invention is described in further details with specific embodiment below, but the present invention is not only limited in detail below in fact Apply example.
Four (dimethylamino) zirconium (Zr (NMe2)4), n-hexane (C6H14), Trimethylsilylcyclopendiene (Me3SiCpH)、 Argon gas (Ar), ozone (O3), oxygen (O2), above-mentioned raw materials or reagent can be obtained by commercially available buying.
Occur multiple parameters in the present invention, such as pressure, temperature, time, concentration, boot speed, corresponding unit (such as Pa, DEG C, h, mol/L, sccm) be unified in the upper limit after mark, such as 1.3~4Pa, -5~5 DEG C, 8~20h, 0.6~0.8mol/L, 40 ~60sccm.It is, of course, also possible to using unit is marked after upper limit value and lower limit value, as 1.3Pa~4Pa, -5 DEG C~5 DEG C, 8h ~20h, 0.6mol/L~0.8mol/L, 40sccm~60sccm.The expression way of both parameter areas, in embodiment In to the upper limit of parameter, two endpoint values of lower limit and intermediate value, all can tape unit after numerical value.Zirconium oxide of the present invention, Zirconium dioxide, Zirconium oxide, ZrO2Meaning is identical, refers both to ZrO2For main component, structure and ZrO2The identical object of crystal structure Matter.Tetramethyl acylamino- zirconium and four (dimethylamino) zirconium meanings are identical, and referring both to structural formula is Zr (NMe2)4Compound.Wen Zhong " with ... for main component " or " including ... " description refer both to be with " ... " main composition substance, can also be with Addition does not influence the other compositions of overall efficacy." substrate " and " sample " refers both to the matrix for deposition film in the present invention.
In implementation process, the presoma SCTDMAZ that can first synthesize sufficient amount is spare, then uses thermal atomic layer deposition method Or the mode deposition film of plasma enhanced atomic layer deposition method, what is obtained is the zirconia film of silicon doping.
Embodiment provided below is not intended to limit the invention covered range, and described step is also not use Sequence is executed to limit its.Those skilled in the art combine existing common knowledge to do conspicuous improvement to the present invention, also fall Enter the present invention claims protection scope within.
Embodiment one
A kind of preparation method of the zirconia film of the silicon doping of high dielectric constant, which comprises the following steps:
1. 37.45g tetramethyl acylamino- zirconium (140mmol) is dissolved in 200mL n-hexane, is obtained in 500ml flask To solution A；
2. by 16.59g Trimethylsilylcyclopendiene (Me3SiCpH, 120mmol) it is dissolved in 30mL n-hexane, it obtains B solution；
3. being slowly dropped into solution A by B solution at 0 DEG C or so and (instilling time control at 30 minutes or so), and in room temperature It persistently stirs 12 hours down；
4. removing n-hexane by vacuum distillation, 40.72g crude product (deep yellow color liquid) can be obtained；
5. crude product can be obtained 34.92g product, i.e. presoma by 2 vacuum distillation (110 DEG C, 2.4Pa) purifications (Me3SiCp)Zr(NMe2)3, three (dimethylamino)-trimethyl silicon substrates-cyclopentadienyl group zirconium, abbreviation SCTDMAZ, yield is about 70%；
6. above-mentioned SCTDMAZ is heated to 70 DEG C, and use argon gas as delivery gas, SCTDMAZ is input to atomic layer In deposition reaction chamber；The temperature that SCTDMAZ is heated to 60~80 DEG C of ranges (including endpoint value) is ok；
7. pumping out excessive presoma using argon gas as purge gas；
8. using ozone as oxidant, uses argon gas as delivery gas, reacted at 350 DEG C；The importing speed of ozone Degree is 150sccm；Oxidant can also be that vapor, delivery gas can also be helium or nitrogen；The importing speed of oxidant Degree is 50~500sccm, including endpoint value；
9. the reaction that repeats the above steps is until obtain the film of required thickness.
The film obtained by above step obtains it with polarised light ellipsometer measurement with a thickness of 25nm, and deposition rate is 1.1A/ the period；(curve of bottom one of Fig. 1) is detected by XRD, it is found that the film deposited is without specific brilliant Body ZrO2Peak, film show preferable amorphous phase；The ratio for showing Zr: Si: O by XPS test is 31.5%: 11.2%: 58.3%；AFM test display, the r.m.s. roughness of film are less than 0.5nm.
With PVD (physical vapour deposition (PVD)) in aluminium (Al) electrode of one layer of 100nm of film disposed thereon, use The dielectric constant and leakage current density of Keithley4200-SCS measurement film.When frequency is 1MHz, above-mentioned ZrSiOxJie Electric constant is 12.7；Under the electric field of 2MV/cm, leakage current density is 1.0 × 10-8A/cm2。
Embodiment two
A kind of preparation method of the zirconia film of the silicon doping of high dielectric constant, which comprises the following steps:
1. 37.45g tetramethyl acylamino- zirconium (140mmol) is dissolved in 200mL n-hexane, is obtained in 500ml flask To solution A；
2. by 19.36g Trimethylsilylcyclopendiene (Me3SiCpH, 140mmol) it is dissolved in 30mL n-hexane, it obtains B solution；
3. being slowly dropped into solution A by B solution at 0 DEG C or so and (instilling time control at 30 minutes or so), and in room temperature It persistently stirs 12 hours down；
4. removing n-hexane by vacuum distillation, 45.25g crude product (deep yellow color liquid) can be obtained；
5. crude product can be obtained 38.80g product SCTDMAZ, yield by 2 vacuum distillation (100 DEG C, 1.3Pa) purifications About 76.8%；
6. above-mentioned SCTDMAZ is heated to 60 DEG C, SCTDMAZ is input in atomic layer deposition reaction chamber with argon gas, It is allowed to be deposited on sample surfaces；
7. pumping out excessive presoma using argon gas as purge gas；
8. use oxygen as the source gas of plasma, use argon gas as delivery gas, 100 DEG C at a temperature of and waiting Ionized gas is reacted in the case where being formed with the presoma of sample surfaces；The boot speed of oxygen is 50sccm；
9. the reaction that repeats the above steps is until obtain the film of required thickness.
Film is obtained by above step, obtains it with polarised light ellipsometer measurement with a thickness of 30nm, deposition rate is 1.2A/ the period；By XRD detection (three curves above Fig. 1), it is found that the film deposited does not have specific crystal ZrO2Peak, film show preferable amorphous phase, and film is annealed 30 minutes at 700 DEG C, still shows preferable amorphous phase；XPS is surveyed It takes temperature bright, Zr: Si: O ratio is 33.5%: 9.0%: 57.5%；AFM test display, the r.m.s. roughness of film are less than 0.2nm (such as Fig. 3).It is 13.7 by the thin-film dielectric constant measured with the identical method of embodiment one；In the electric field of 2MV/cm Under, leakage current density is 1.1 × 10-8A/cm2。
Embodiment three
A kind of preparation method of the zirconia film of the silicon doping of high dielectric constant, which comprises the following steps:
1. 37.45g tetramethyl acylamino- zirconium (140mmol) is dissolved in 200mL n-hexane, is obtained in 500ml flask To solution A；
2. by 19.36g Trimethylsilylcyclopendiene (Me3SiCpH, 140mmol) it is dissolved in 30mL n-hexane, it obtains B solution；
3. being slowly dropped into solution A by B solution at -5 DEG C or so and (instilling time control at 30 minutes or so), and in room temperature It persistently stirs 12 hours down；
4. removing n-hexane by vacuum distillation, 45.25g crude product (deep yellow color liquid) can be obtained；
5. crude product can be obtained 38.80g product SCTDMAZ, yield is about by 2 vacuum distillation (110 DEG C, 3Pa) purifications 76.8%；
6. above-mentioned SCTDMAZ is heated to 80 DEG C, SCTDMAZ is input in atomic layer deposition reaction chamber with argon gas, It is allowed to be deposited on sample surfaces；
7. pumping out excessive presoma using argon gas as purge gas；
8. using N2Source gas of the O as plasma, use helium as delivery gas, 220 DEG C at a temperature of and waiting Ionized gas is reacted in the case where being formed with the presoma of sample surfaces；N2The boot speed of O is 250sccm；
9. the reaction that repeats the above steps is until obtain the film of required thickness.
The film obtained by above step obtains it with polarised light ellipsometer measurement with a thickness of 29nm, and deposition rate is 1.2A/ the period.XPS test shows that Zr: Si: O ratio is 33.0%: 10.2%: 56.8%.AFM test display, film R.m.s. roughness is less than 0.5nm.It is 13.5 by the thin-film dielectric constant measured with the identical method of embodiment one；In 2MV/ Under the electric field of cm, leakage current density is 1.0 × 10-8A/cm2。
Example IV
A kind of preparation method of the zirconia film of the silicon doping of high dielectric constant, which comprises the following steps:
1. 37.45g tetramethyl acylamino- zirconium (140mmol) is dissolved in 200mL n-hexane, is obtained in 500ml flask To solution A；
2. by 19.36g Trimethylsilylcyclopendiene (Me3SiCpH, 140mmol) it is dissolved in 30mL n-hexane, it obtains B solution；
3. being slowly dropped into solution A by B solution at 5 DEG C or so and (instilling time control at 30 minutes or so), and in room temperature It persistently stirs 12 hours down；
4. removing n-hexane by vacuum distillation, 45.25g crude product (deep yellow color liquid) can be obtained；
5. crude product can be obtained 38.80g product SCTDMAZ, yield is about by 2 vacuum distillation (120 DEG C, 4Pa) purifications 76.8%；
6. above-mentioned SCTDMAZ is heated to 70 DEG C, SCTDMAZ is input in atomic layer deposition reaction chamber with argon gas, It is allowed to be deposited on sample surfaces；
7. pumping out excessive presoma using argon gas as purge gas；
8. using CO2As the source gas of plasma, use argon gas as delivery gas, 300 DEG C at a temperature of and waiting Ionized gas is reacted in the case where being formed with the presoma of sample surfaces；CO2Boot speed be 500sccm；
9. the reaction that repeats the above steps is until obtain the film of required thickness；
10. obtained film is annealed 30 minutes at 700 DEG C.
Film is obtained by above step, obtains it with polarised light ellipsometer measurement with a thickness of 30nm, deposition rate is 1.2A/ the period.It is 15.1 by the thin-film dielectric constant measured with the identical method of embodiment one；Under the electric field of 2MV/cm, Leakage current density is 3.2 × 10-8A/cm2。

Claims (10)

1. the preparation method for the zirconia film that a kind of silicon of high dielectric constant adulterates, which is characterized in that use (Me3SiCp)Zr (NMe2)3As at least one presoma, pass through thermal atomic layer deposition method or the side of plasma enhanced atomic layer deposition method Formula deposits the zirconia film of silicon doping；Wherein Cp represents cyclopentadienyl group, and Me is methyl.
2. the preparation method of the zirconia film of the silicon doping of high dielectric constant according to claim 1, which is characterized in that only Using (Me3SiCp)Zr(NMe2)3Unique a kind of presoma as element silicon and zr element source.
3. the preparation method of the zirconia film of the silicon doping of high dielectric constant according to claim 1, which is characterized in that institute State (Me3SiCp)Zr(NMe2)3Synthetic method the following steps are included:
1) tetramethyl acylamino- zirconium is dissolved in n-hexane, obtains solution A；
2) Trimethylsilylcyclopendiene is dissolved in n-hexane, obtains B solution；
3) B solution is slowly dropped into solution A at -5~5 DEG C, is continuously stirred at room temperature；
4) it is evaporated under reduced pressure under conditions of temperature is 100~120 DEG C, pressure is 1.3~4Pa, removes n-hexane, slightly produced Product；
5) crude product is purified by 1~4 vacuum distillation to get (Me3SiCp)Zr(NMe2)3。
4. the preparation method of the zirconia film of the silicon doping of high dielectric constant according to claim 3, which is characterized in that four The ratio between amount of substance of methylamido zirconium and Trimethylsilylcyclopendiene is 1: (0.8~1.0).
5. the preparation method of the zirconia film of the silicon doping of high dielectric constant according to claim 1, which is characterized in that institute State thermal atomic layer deposition method the following steps are included:
1) by presoma (Me3SiCp)Zr(NMe2)3It is heated to 60~80 DEG C, and with the inert gas comprising argon gas or nitrogen As delivery gas, by (Me3SiCp)Zr(NMe2)3It is input in atomic layer deposition reaction chamber；
2) using the inert gas comprising argon gas or nitrogen as purge gas, excessive presoma is pumped out；
3) make oxidant as main component to ozone or vapor, with the inert gas comprising helium, argon gas or nitrogen As delivery gas, 200~500 DEG C at a temperature of reacted；
4) reaction is repeated the above steps until obtaining the film of required thickness.
6. the preparation method of the zirconia film of the silicon doping of high dielectric constant according to claim 5, which is characterized in that institute The boot speed for stating oxidant is 50~500sccm.
7. the preparation method of the zirconia film of the silicon doping of high dielectric constant according to claim 1, which is characterized in that institute State plasma enhanced atomic layer deposition method the following steps are included:
1) by presoma (Me3SiCp)Zr(NMe2)360~80 DEG C are heated to, with the indifferent gas comprising helium, argon gas or nitrogen Body, by (Me3SiCp)Zr(NMe2)3It is input in atomic layer deposition reaction chamber, is allowed to be adsorbed on substrate surface；
2) using the inert gas comprising helium, argon gas or nitrogen as purge gas, excessive presoma is pumped out；
3) source gas to oxygen, nitrous oxide or carbon dioxide gas as main component as plasma is used Inert gas comprising helium, argon gas or nitrogen as delivery gas, 100~300 DEG C at a temperature of and in plasma (orifice) gas Body is reacted in the case where being formed with the presoma adsorption component of substrate surface；
4) reaction is repeated the above steps until obtaining the film of required thickness.
8. the preparation method of the zirconia film of the silicon doping of high dielectric constant according to claim 7, which is characterized in that institute The boot speed for stating the source gas of plasma is 50~500sccm.
9. the zirconia film that a kind of silicon of high dielectric constant adulterates, which is characterized in that using such as any one of claim 1-8 institute The preparation method stated obtains.
10. the zirconia film that the silicon of high dielectric constant according to claim 9 adulterates, which is characterized in that the film Surface roughness≤0.5nm.
CN201811420812.6A 2018-11-27 2018-11-27 A kind of preparation method and its product of the zirconia film of the silicon doping of high dielectric constant Withdrawn CN109338331A (en)

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Citations (2)

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CN102712662A (en) * 2009-08-14 2012-10-03 乔治洛德方法研究和开发液化空气有限公司 Hafnium- and zirconium-containing precursors and methods of using the same
CN107210219A (en) * 2014-12-23 2017-09-26 乔治洛德方法研究和开发液化空气有限公司 The formation composition of the film containing zirconium for the film containing zirconium that is vapor-deposited

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Publication number Priority date Publication date Assignee Title
CN102712662A (en) * 2009-08-14 2012-10-03 乔治洛德方法研究和开发液化空气有限公司 Hafnium- and zirconium-containing precursors and methods of using the same
CN107210219A (en) * 2014-12-23 2017-09-26 乔治洛德方法研究和开发液化空气有限公司 The formation composition of the film containing zirconium for the film containing zirconium that is vapor-deposited

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