WO2003035926A2 - Improved precursors for chemical vapour deposition - Google Patents

Improved precursors for chemical vapour deposition Download PDF

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WO2003035926A2
WO2003035926A2 PCT/GB2002/004822 GB0204822W WO03035926A2 WO 2003035926 A2 WO2003035926 A2 WO 2003035926A2 GB 0204822 W GB0204822 W GB 0204822W WO 03035926 A2 WO03035926 A2 WO 03035926A2
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precursor
alkyl group
mmp
ligand
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PCT/GB2002/004822
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WO2003035926A3 (en
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Anthony Copeland Jones
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Epichem Limited
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Priority claimed from GB0125724A external-priority patent/GB0125724D0/en
Priority claimed from GB0129080A external-priority patent/GB0129080D0/en
Application filed by Epichem Limited filed Critical Epichem Limited
Priority to JP2003538422A priority Critical patent/JP4472338B2/en
Priority to DE60215034T priority patent/DE60215034T2/en
Priority to EP02772548A priority patent/EP1438315B1/en
Priority to US10/493,667 priority patent/US7419698B2/en
Priority to DE02772548T priority patent/DE02772548T1/en
Priority to AU2002337310A priority patent/AU2002337310A1/en
Publication of WO2003035926A2 publication Critical patent/WO2003035926A2/en
Publication of WO2003035926A3 publication Critical patent/WO2003035926A3/en

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic System
    • C07F5/003—Compounds containing elements of Groups 3 or 13 of the Periodic System without C-Metal linkages
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic System
    • C07F7/003—Compounds containing elements of Groups 4 or 14 of the Periodic System without C-Metal linkages

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Vapour Deposition (AREA)
  • Crystals, And After-Treatments Of Crystals (AREA)
  • Gas Separation By Absorption (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Formation Of Insulating Films (AREA)

Abstract

Ti, Zr Hf and La precursors for use in MOCVD techniques have a ligand of the general formula OCR1(R2)CH2X, wherein R1 is H or an alkyl group, R2 is an optionally substituted alkyl group and X is selected from OR and NR¿2?, wherein R is an alkyl group or a substituted alkyl group.

Description

Improved precursors for chemical vapour deposition
Description
This invention concerns precursors for chemical vapour deposition. This invention is particularly, but not exclusively concerned with precursors for the growth of zirconium oxide (ZrO2), hafnium oxide (HfO2), zirconium oxide/silicon oxide (ZSO) and hafnium oxide/silicon oxide (HSO) by chemical vapour deposition.
Thin films of ZrO2 and Hf02 and the related silicates ZSO and HSO have important technological applications. In particular, they have high permittivities and are relatively stable in contact with silicon, making them the prime candidates to replace Si02 as gate dielectric layers in next-generation MOSFET devices in integrated Si circuits. Metalorganic chemical vapour deposition (MOCVD) is an attractive technique for the deposition of these materials, offering the potential for large area growth, good composition control and film uniformity, and excellent conformal step coverage at device
dimensions less than 2μm, which is particularly important in microelectronics
applications.
An essential requirement for a successful MOCVD process is the availability of precursors with the appropriate physical properties for vapour phase transport and a suitable reactivity for deposition. There must be an adequate temperature window between evaporation and decomposition, and for most electronics applications oxide deposition is restricted to temperatures in the region of 500°C, to prevent degradation of the underlying silicon circuitry and metal interconnects.
There are a number of problems associated with existing Zr and Hf
CVD precursors. For instance, the halides ZrCI4 and HfCI4 are low volatility solids which need substrate temperatures of 800°C and above for oxide
deposition. Metal β-diketonates, such as [Zr(thd)4] (thd = 2,2,6,6- tetramethylheptane-3,5-dionate) also require high substrate temperatures (>
600°C) for oxide growth. These are incompatible with the requirements of the electronics industry. Metal alkoxides are more attractive CVD precursors as
they allow lower deposition temperatures. However, the majority of [Zr(OR)4]
and [Hf(OR)4] complexes are dimeric or polymeric with limited volatility, due to the pronounced tendency of the Zr(IV) and Hf(IV) to expand their coordination sphere to six, seven or eight. In order to inhibit oligomerisation, sterically demanding ligands such as ferf-butoxide have been employed, and
[Zr(OBu4)4] (D.C. Bradley, Chem. Rev. 1989, 89, 1317) and [Hf(OBu ] (S.
Pakswer & P Skoug, in " Thin dielectric oxide films made by oxygen assisted pyrolysis of alkoxides", The Electrochem. Soc, Los Angeles, CA, USA, 1970,
619 - 636) have been successfully used for the CVD of Zr02 and HfO2.
However, these mononuclear precursors contain unsaturated four-coordinate metal centres and the ferf-butoxide ligand undergoes a catalytic decomposition reaction in the presence of trace water. This makes them highly air and moisture sensitive and susceptible to pre-reaction in the CVD reactor. Their reactivity also leads to a greatly reduced shelf life, especially in solution-based liquid injection CVD applications. An object of this invention is to provide stable and volatile Ti, Zr and Hf precursors suitable for use in chemical vapour deposition techniques.
It has been surprisingly found that the donor functionalised alkoxy ligand 1-methoxy-2-methyl-2-propanolate [OCMe2CH2OMe, mmp] is effective in inhibiting oligomerisation in Zr and Hf alkoxide complexes, as well as increasing the ambient stability of the complexes.
Accordingly the present invention provides Ti, Zr, Hf and La precursors for use in MOCVD techniques having a ligand of the general formula OCR1(R2)CH2X, wherein R1 is H or an alkyl group, R2 is an optionally substituted alkyl group and X is selected from OR and NR2,wherein R is an alkyl group or a substituted alkyl group.
Precursors according to a first preferred embodiment of the invention have the following general formula:
M(L)x[OCR1(R2)CH2X]4-χ
wherein M is a metal selected from Ti, Zr and Hf, L is a ligand, x is a number from 0 to 3 and R1, R2 and X are as defined above.
The preferred ligand L is an alkoxy group having from 1 to 4 carbon atoms, of which tertiary-butoxide (OBu1) group is most preferred, although other groups such as iso-propoxide (OPr1) can be employed.
The preferred ligand of the formula OCR1(R2)CH2X is 1-methoxy-2- methyl-2-propanolate (mmp) but other donor functionalised alkoxide ligands may also carry out the desirable function of inhibiting oligomerisation in Zr, Hf and Ti alkoxides for use in the invention. These include but are not limited to OCH(Me)CH2OMe, OCEt2CH2OMe, OCH(But)CH2OEt, OC(But)2CH2OEt,
OC(Pιj)2CH2OEt, OCH(But)CH2NEt2, OC(Pι )2CH2OC2H4OMe and
OC(But)(CH2OPri)2 .
The invention further provides a method of making Ti, Zr and Hf precursors for use in MOCVD techniques comprising reacting mmpH with the corresponding metal alkoxide or metal alkylamide in appropriate molar proportions.
The new alkoxide complexes Zr(OBut)2(mmp)2, Zr(mmp)4, Hf(OBut)2(mmp)2, and Hf(mmp)4 have been synthesised by the addition of mmpH to Zr(OBul)4 and Hf(OBu')4 in appropriate molar proportions. The complexes have high vapour pressures suitable for MOCVD, and are also much less reactive to air and moisture than Zr(OR)4 compounds, wherein R is an alkyl group, making them easier to handle and use in MOCVD. The reduced air-sensitivity of these new Zr and Hf complexes arises from the replacement of the highly moisture sensitive terf-butoxide groups in [Z^OBu^] and [H^OBu^] with the mmp ligand, which is much less susceptible to hydrolysis. The complexes are further stabilised to hydrolysis by an increase in the coordination number of the central Zr or Hf atom.
According to a second preferred embodiment the invention can be extended to other metals, which have large atomic radii and are highly positively charged, such as lanthanum, in which case preferred precursors have the following general formula
Figure imgf000005_0001
wherein R1 is H or an alkyl group, R2 is an optionally substituted alkyl group and X is selected from OR and NR2,wherein R is an alkyl group or a substituted alkyl group.
The preferred ligand for this preferred embodiment of the invention is 1-methoxy-2-methyl-2-propanolate [OCMe2CH2OMe], although other donor functionalised alkoxide ligands may be used. These may include but are not limited to OCH(Me)CH2OMe, OCEt2CH2OMe, OCH(But)CH2OEt, OC(But)2CH2OEt, OC(PrJ)2CH2θEt> OCH(But)CH2NEt2, OC(Pri)2CH2θC2H4OMe and OC(ButχCH2OPri)2 .
The invention also provides a preferred method of making precursors according to the second preferred embodiment comprising reacting mmpH with La{N(SiMe3)2}3 in appropriate molar proportions.
Precursors according to the invention may be used in depositing single or mixed oxide layers or films by conventional MOCVD, in which the precursor is contained in a metalorganic bubbler, or by liquid injection MOCVD, in which the precursor is dissolved in an appropriate inert organic solvent and then evaporated into the vapour phase using a heated evaporator. The precursors may also be suitable for use in the deposition of zirconium oxide, hafnium oxide and titanium oxide films by other chemical vapour deposition techniques, such as atomic layer deposition (ALD).
The precursors can be used for the MOCVD of Zr02, HfO2, and Ti02, La2O3, and in combination with other precursors for the MOCVD of complex oxides containing zirconium oxide, hafnium oxide, and lanthanum oxide such as ZSO and HSO and La-silicate.
The precursors can also be used in combination for the MOCVD of complex oxides. Examples include the MOCVD of bismuth-titanate from the combinations Bi(mmp)3 / Ti(OPri)2(mmp)2 or Bi(mmp)3 / Ti(mmp)4.
The invention will now be further described with reference to the accompanying drawings, in which:
Figure 1 shows an envisaged structure for M(OBut)2(mmp)2 (M = Zr or Hf);
Figure 2 shows the molecular structure of Hf(mmp)4. Zr(mmp)4 has a similar structure; and
Figure 3 shows laser Raman spectra Zrθ2 and Hfθ2 films grown by liquid injection MOCVD using Zr(OBut)2(mmp)2 or Hf(OBut)2(mmp)2.
The invention will now be further described by means of the following Examples.
Example 1
Preparation of Zr(OBul)2(mmp)2
2.8 ml (2.69 g, 7.0 mmol) Z^OBu^ was dissolved in hexane (ca. 40 ml). mmpH (1.6 ml, 1.44 g, 13.9 mmol) was added dropwise, the mixture was heated to reflux and stirring continued for a further 2 hours. The solution was cooled to room temperature and the volatiles removed by evaporation under reduced pressure. The product was recrystallised from hexane to give a white crystalline solid.
M.pt.: 96 - 101 °C (uncorrected) Microanalysis: Calc. C: 48.71 , H: 9.10. Found: C: 46.32, H: 8.77%
1H NMR: (400MHz, dβ-tol) 1.19 (s, 12H,
Figure imgf000008_0001
1.37 (s, 18H,
OC(Ctk ), 3.23 (s, 4H, O CHskCHgOCHs), 3.40 (s, 6H,
O CHskCHsOCHsJ.
13C NMR: 34.1 (OCfCH^CHzOCHs), 38.5 (OC(CH3)3), 65.4
(OC(CH3)2CH2OCH2), 78.6 (OC(CH3)2CH2OCH3 and OC(CH3)3), 90.5
Figure imgf000008_0002
IR: (υ cm"1, Nujol, NaCI) 3588(w), 3442(w), 2725(m), 2360(w), 1356(s),
1277(m), 1227(m), 1206(s), 1177(s), 1115(s), 1080(s), 1012(s), 974(s),
936(s), 801 (s), 782(s), 595(s).
An envisaged structure for Zr(OBut)2(mmp)2 is shown in Figure 1 of the drawings.
Example 2
Preparation of Zr(mmp)4
2.0 g (5.2 mmol) Zr(OPri)4»PriOH was dissolved in hexane (ca. 40 ml).
mmpH (2.6 ml, 2.35 g, 22.5 mmol) was added dropwise, the mixture heated to reflux and stirring was continued for 2 hours. The mixture cooled to room temperature and the volatiles was removed by evaporation under reduced pressure to give the product as a white viscous oil. (Yield: 2.4 g, 94%).
Zr(mmp)4 can also be synthesised from the corresponding zirconium alkylamide complexes, Zr(NR2)4. For instance, by the dropwise addition of mmpH (6.9g, 65.8 mmol) to a stirred solution of [Zr(NEt2)4j ( 5.0g, 13.2 mmol) in hexane (50 cm3). The mixture was boiled under reflux for 2 hr. and then allowed to cool to room temperature. Volatiles were removed in vacuo to give the product (yield 6.25 g, 94%).
Microanalysis: Calc. C: 47.67, H: 8.82 Found: C:47.80, H: 8.79%.
1H NMR: (400 MHz, d8-tol): 1.21 (s, OC(CH3)2CH2OCH3), 3.16 (s,
OC(CH3)2CH2OCH3), 3.27 (s, OC(CH3)2CH20 Ctk)
13C NMR: (100 MHz, d8-tol): 32.1 (OC(CH2)2C 2OC 3), 64.8
(OC(CH3)2C 2OCH2), 76.0 (OC(CH3)2CH2OCH3), 88.5 (OC(CH3)2CH OCH3).
IR: (υ crrϊ1, Nujol, NaCI) 3589(w), 3448(w,br), 2724(m), 2346(w), 1377(s),
1322(m), 1279(m), 1239(m), 1176(s), 1134(m), 1114(s), 1081(m), 1018(s),
996(m), 982(s), 958(m), 937(m), 917(m), 845(m), 804(m), 784(m), 594(s).
Example 3
Preparation of Hf(OBut)2(mmp)2
3.5 ml (4.0 g, 8.5 mmol) HfiOBu*^ was dissolved in hexane (ca. 40 ml) to give a yellow solution. MmpH (2.0 ml, 1.79 g, 19.0 mmol) was added dropwise, the mixture heated to reflux and stirring continued for 2 hours. The solution was allowed to cool and the volatiles removed by boiling under reduced pressure. The crude product was recrystallised from hexane to give a white crystalline solid. (Yield: 4.4 g, 97%).
M. Pt: 100 - 104 ° C (uncorrected)
Microanalysis: Calc. C: 40.71 , H: 7.61. Found. C: 38.93, H: 7.30%
1H NMR: (400 MHz, d8-tol): δ = 1.18 (s, 12H, OC(CH2)2C 2OC 3), 1.38 (s,
18H, OC(CH2)3), 3.21 (s, 12H, OC(CH3)2CH2OCH3)> 3.42 (s, 12H, OC(CH3)2CH2θCH2) 13C NMR: (100 MHz d8-tol): δ = 34.4 (OC(Cr^)2CH2OCH3), 38.6 OC&Hs ),
65.7, (OC(CH3)2CH2OCH ), 78.0, 79.1 (OC(CH3)2CH2OCH3 and OC(CH3)3), 90.9 (OC(CH3)2CH2OCH3),
IR: (υ cm"1, Nujol, NaCI): 3441 (w), 2726(m), 2256(w), 1272(s), 1177(s),
1074(s), 1016(s), 976(s), 802(s), 782(s), 593(s).
An envisaged structure for Hf(OBut)2(mmp)2 is shown in Figure 1 of the drawings.
Example 4
Preparation of Hf(mmp)4
4.0 ml (5.56 g, 11.9 mmol) [Hf(NEt2)4] was dissolved in hexane (60 ml). Hmmp (7.0 ml, 6.3 g, 60 mmol) was added dropwise and the mixture refluxed for 90 mins. Volatiles were removed in vacuo to give the product as a yellow viscous oil.
(Yield: 6.88 g, 97.5 %).
Microanalysis: Calc. C: 40.63, H: 7.52. Found. C39.85, H 7.32% 1H NMR: 1.30 (s, 24H, O CHskCHzOCHs), 3.28 (s, 8H, OC(CH3)2CH2θCH- 3), 3.36 (s, 12H, OC(CH3)2CH2OCH^)
13C NMR: 34.74 (OC(CH3)2CH2OCH3), 65.16 (OC(CH3)2CH2OCH3), 79.83 (OC(CH3)2CH2OCH3), 90.25 (OC(CH3)2CH2OCH3)
IR: (Nujol/NaCI): 3585(w), 3450(w,br), 2722(m), 1366(s), 1356(vs), 1268(s), 1242(s), 1214(vs), 1177(vs), 1115(vs), 1079(vs), 1045(vs), 1026(vs), 996(vs), 975(vs), 936(vs), 912(m), 802(s), 779(s), 594(vs).
An envisaged structure for Hf(mmp)4 is shown in Figure 2 of the accompanying drawings. Example 5
Preparation of Zr(OPri)2(mmp)2
1.06 g (2.75 mmol) Zr(OPri)4»PriOH was dissolved in hexane (ca 40
ml). 1-methoxy-2-methyl-2-propanol [mmpH] (0.65 ml, 0.57 g, 5.5 mmol) was added dropwise, the mixture was heated to reflux and stirring continued for a further 2 hours. The solution was cooled to room temperature and the volatiles removed by evaporation under reduced pressure. The product was isolated as a white viscous oil.
Microanalysis: Calc. C: 46.23, H: 8.73. Found: C: 44.17, H: 8.47 1H NMR (400MHz, d8-tol): 1.26 (s, OC(CJ&)2CH2OCH3), 1.32 (d, OCH(CH3)2), 3.26 (2, OC(CH3)2CH2θCH3), 3.36 (s, OC(CH3)2CH2OCH3), 4.46 (m,
OCH(CH3)2).
13C NMR (100MHz, d8-tol): 32.1
Figure imgf000011_0001
34.2 (OCH(CH2)2), 64.9
Figure imgf000011_0002
76.1 , 76.4 (OCH(CH3)2 and OC(CH3)2CH2OCH3), 88.6 (OC(CH3)2CH2OCH3).
IR: (υ cm"1, Nujol, NaCI) 3589(w), 3423(w), 2724(w), 2282(w), 1239(w),
1175(m), 1115(m), 1019(m), 959(m).
Example 6
Preparation of Ti(OPri)2(mmp)2 MmpH (2.81 g, 27mmol) was added dropwise to 0.0135moles) to a stirred solution of Ti(OPri)4 (3.84g, 13.5mmol) in hexane (20 ml). The mixture was boiled under reflux for 11/2 hours and was then allowed to cool. The solvent was then removed in vacuo to give Ti(OPri)2(mmp)2 as a colourless oil. Microanalysis for TiC16H36θ4 : (calculated) C% 51.61 , H% 9.75;
(experimental) C% 51.20, H% 9.92.
1H NMR (C6D5CD3 at 30°C) δ 1.1 (26H, d, (CH3)2CH; CH3OCH2(CH3)2C ); δ
3.2 ( 10H, two singlets, CH3OC fe(CH3)2C ); δ 4.5 ( 2H, m, (CH3)2CH ).
3C{1H> NMR (C6D5CD3, 30°C): 32 (OC(CH3)2CH2OCH3), 33.4 (OC (C\-\2)2),
64.4 (OC(CH3)2CH2OCH5), 81.7 (OC(CH3)2CH2OCH3 86.5 (OCH(CH3)2), 88
Figure imgf000012_0001
IR (Nujol, cm"1) 2972s, 2928s, 2869s, 2625w, 1463m, 1376m, 1360s, 1331m,
1277m, 1126s, 1001s, 850s, 778m., 629s.
Example 7
Preparation of Ti(mmp)4 MmpH (4.41 g, 42 mmol) was added dropwise to a stirred solution of Ti(NEt2) (2.85g; 3ml; 8.47mmole) in hexane (20 ml) resulting in pale brown solution. The mixture was boiled under reflux for 11/2 hours, allowed to cool, and then volatiles were removed in vacuo to give Ti (mmp)4 as a pale brown oil. Microanalysis for TiCaoHφ j : (calculated) C% 52.17, H% 9.63; (experimental) C% 51.95, H% 9.97.
1H NMR (C6D5CD3 at 30°C) δ 1.3 (24H, s, CH3OCH2(CH3)2C ); δ 3.2 ( 20H,
two singlets, CH3OCH2.(CH3)2C). VT 1H NMR showed sharp distinct peaks
from -50 to +50 °C - no broadening was apparent.
13C{1H> NMR (C6D5CD3, 30°C): 31.9 (OCCCH^ChbOCHs), 64.5
(OC(CH3)2CH2OCH3), 81.7 (OC(CH3)2CH2OCH3), 87 (OC(CH3)2CH2OCH3). IR (Nujol, cm"1) 2975s, 2931s, 2876s, 2829m, 2625w, 1461m, 1360s, 1331m, 1277m, 12406m, 1116s, 1004s, 850m., 796s, 775s, 625s. Example 8
Preparation of La(mmp)3 [La{N(SiMe3)2}3] (2.89 g, 4.6 mmol) was dissolved in toluene (50 ml) and mmpH (2.2 ml, 1.96 g, 18.7 mmol) added dropwise under stirring. Stirring was continued at room temperature for a further 21 hours and the volatiles removed in vacuo to give the product as a brown viscous oil (Yield = 1.8 g , 87% with respect to La)
Microanalysis for LaC15H33θ6(calculated) C % 40.18, H % 7.43; (experimental) C % 40.01 , H % 7.38
Example 9
Zirconium oxide and hafnium oxide deposition from Zr(OBut)2(mmp)2, Zr(mmp)4, Hf(OBut)2(mmp)2 and Hf(mmp)4
All four complexes were found to be excellent precursors for the deposition of ZrO2 and Hf0 thin films by MOCVD. The Zr02 and HfO2 films were deposited by liquid injection MOCVD using the same general conditions shown in Table 1 below.
Table 1 Growth conditions used for the growth of Zr02 or Hf02 thin films by liquid injection MOCVD using Zr(OBut)2(mmp)2, Zr(mmp)4, Hf(OBut)2(mmp)4 or Hf(mmp)4
Figure imgf000014_0001
The identity of the films was confirmed as Zr02 or Hf02 by laser Raman spectroscopy (see Figure 3). Raman spectra of Zrθ2 and Hfθ2 films grown from Zr(OBut)2(mmp)2 or Hf(OBut)2(mmp)2 are shown in Fig. 3. Comparison
with bulk crystalline data showed that these films were predominantly in the α-
or monoclinic phase.

Claims

1. Ti, Zr, Hf and La precursors for use in MOCVD techniques having a ligand of the general formula OCR1(R2)CH2X, wherein R1 is H or an alkyl group, R2 is an optionally substituted alkyl group and X is selected from OR and NR2, wherein R is an alkyl group or a substituted alkyl group.
2. A precursor for use in MOCVD techniques having the following general formula:
M(L)x[OCR1(R2)CH2X]4.x
wherein M is a metal selected from Ti, Zr and Hf, L is a ligand, x is a number from 0 to 3 and R1, R2 and X are as defined above.
3. A precursor as claimed in claim 2, wherein the ligand L is an alkoxy group having from 1 to 4 carbon atoms.
4. A precursor as claimed in claim 3, wherein the ligand L is selected from tertiary-butoxide (OBu*) and iso-propoxide (OPH).
5. A precursor as claimed in any one of claims 1 to 4, wherein the ligand of the formula OCR1(R2)CH2X is 1-methoxy-2-methyl-2-propanolate (mmp).
6. A precursor as claimed in any one of claims 1 to 4, wherein the ligand of the formula OCR1(R2)CH2X is selected from OCH(Me)CH2OMe, OCEt2CH2OMe, OCH(But)CH2OEt, OC(But)2CH2OEt, OC(Pri)2CH2OEt, OCH(But)CH2NEt2, OC(Pri)2CH2OC2H4OMe and OC(But)(CH2OPri)2 .
7. Zr(OBut)2(mmp)2.
8. Zr(mmp) .
Figure imgf000016_0001
10. Hf(mmp)4
11. A method of making Ti, Zr and Hf precursors for use in MOCVD techniques comprising reacting HOCR1(R2)CH2X with the corresponding metal alkoxide or metal alkylamide in appropriate molar proportions.
12. A precursor for use in MOCVD techniques having the following general formula
La[OCR1(R2)CH2X]3 wherein R1 is H or an alkyl group, R2 is an optionally substituted alkyl group and X is selected from OR and NR2,wherein R is an alkyl group or a substituted alkyl group.
13. A precursor as claimed in claim 12, wherein the ligand is 1-methoxy-2- methyl-2-propanolate [OCMe2CH2OMe].
14. A precursor as claimed in claim13, wherein the ligand is selected from OCH(Me)CH2OMe, OCEt2CH2OMe, OCH(But)CH2OEt, OC(But)2CH2OEt, OC(Pri)2CH2OEt, OCH(But)CH2NEt2) OC(Pri)2CH2OC2H4OMe and OC(But)(CH2OPιJ)2 .
15. La[mmpJ3.
16. A method of making precursors as claimed in claim 12 comprising reacting HOCR1(R2)CH2X with La{N(SiMe3)2}3 in appropriate molar proportions.
17. A method of depositing single or mixed oxide layers or films by conventional MOCVD, in which the precursor is contained in a metalorganic bubbler, or by liquid injection MOCVD, in which the precursor is dissolved in an appropriate inert organic solvent and then evaporated into the vapour phase using a heated evaporator, wherein at least one of the precursors is as defined in any one of claims 1 to 10 and 12 to 15.
PCT/GB2002/004822 2001-10-26 2002-10-25 Improved precursors for chemical vapour deposition WO2003035926A2 (en)

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Application Number Priority Date Filing Date Title
JP2003538422A JP4472338B2 (en) 2001-10-26 2002-10-25 An improved precursor for chemical vapor deposition.
DE60215034T DE60215034T2 (en) 2001-10-26 2002-10-25 PROVISIONAL COMPOUNDS FOR CHEMICAL STEAM PHASE SEPARATION
EP02772548A EP1438315B1 (en) 2001-10-26 2002-10-25 Improved precursors for chemical vapour deposition
US10/493,667 US7419698B2 (en) 2001-10-26 2002-10-25 Precursors for chemical vapor deposition
DE02772548T DE02772548T1 (en) 2001-10-26 2002-10-25 PRECURSOR CONNECTIONS FOR CHEMICAL VAPOR PHASE DEPOSITION
AU2002337310A AU2002337310A1 (en) 2001-10-26 2002-10-25 Improved precursors for chemical vapour deposition

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GB0125724A GB0125724D0 (en) 2001-10-26 2001-10-26 Improved precursors for metalorganic chemical vapour deposition
GB0125724.5 2001-10-26
GB0129080A GB0129080D0 (en) 2001-12-04 2001-12-04 Improved precursors for chemical vapour deposition
GB0129080.8 2001-12-04

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US9583335B2 (en) 2006-06-02 2017-02-28 L'Air Liquide, Société Anonyme pour l'Etude et l'Exploitation des Procédés Georges Claude Method of forming dielectric films, new precursors and their use in semiconductor manufacturing
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US8668957B2 (en) 2006-06-02 2014-03-11 L'Air Liquide, Société Anonyme pour l'Etude et l'Exploitation des Procédés Georges Claude Method of forming dielectric films, new precursors and their use in semiconductor manufacturing
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US7816278B2 (en) 2008-03-28 2010-10-19 Tokyo Electron Limited In-situ hybrid deposition of high dielectric constant films using atomic layer deposition and chemical vapor deposition
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JP4472338B2 (en) 2010-06-02
JP2005506387A (en) 2005-03-03
DE60215034T2 (en) 2007-04-05
CN1571790A (en) 2005-01-26
AU2002337310A1 (en) 2003-05-06
DE60215034D1 (en) 2006-11-09
US7419698B2 (en) 2008-09-02
CN100379745C (en) 2008-04-09
EP1438315A2 (en) 2004-07-21
ATE340800T1 (en) 2006-10-15
DE02772548T1 (en) 2004-11-11
US20050008781A1 (en) 2005-01-13
WO2003035926A3 (en) 2003-06-12

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