TWI275657B - Improved precursors for chemical vapour deposition - Google Patents

Abstract

Ti, Zr, Hf and La precursors for use in MOCND 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 NR2, wherein R is an alkyl group or a substituted alkyl group.

Description

1275657 IX. Description of the Invention: [Technical Field] The present invention relates to the improvement of the precursor of chemical vapor deposition, _ is the use of vaporization and vapor deposition to grow trioxide (r02), dioxin 2), Oxygen-prepared cerium oxide (ZSO) and cerium oxide/cerium oxide (HS0) are required to be precursors, but not limited to this. [Prior Art] According to 'dioxygenation, dioxygenation and its associated zso and HS0 asahi compound films have important considerations, especially he has a high dielectric constant, and the transfer # is very stable, making them Becoming the first place to replace the dioxo as a free-form for the new generation of MOSFET devices in the production of gift circuits. The deposition of these substances by the secret gas vapor deposition method is very attractive, and it has the potential to provide large-area growth, good composition control, uniform film, and device of less than size with excellent, layered coverage. This is especially important in microelectronics. A successful metal organic chemical vapor deposition (M〇CVD) process requires that the precursors used have appropriate physical properties for gas phase transfer and appropriate reactivity for deposition. At the same time, there must be a fine temperature window between gasification and deposition. In most electronic applications, the temperature window of oxide deposition is usually limited to 5〇〇C to avoid the degradation of the performance of the integrated circuit and metal. Internally connected to each other. There are some problems in the known Zr and Hf chemical vapor deposition methods. For example, halides such as antimony tetrachloride and antimony tetrachloride are low-volatile solids, and the temperature of the substrate must be 800 ° C or above. The oxide is deposited thereon; the metal diacetate is cold-diketonates, such as [Zr(thd)4] rush (1=2, 2, 6, 6 7 plus 11^% 11 which 1 & 1 to -3,5 〇1^6) also requires high temperature (>6〇〇) 1275657 substrate for oxide growth, which does not meet the requirements of the electronics industry. Although metal alkoxides are favored for lower deposition temperatures, most of the [Zr(0R)4] and [Hf(OR)4] complexes are di- or multi-molecules with limited volatility. Because it is foreseeable that Zr(IV) and Hf(IV) tend to expand their coordination number to 6, 7 or 8. In order to prevent polymerization, anti-polymeric ligands such as tert-butoxide have been used 'where [Zr(OBu)4] (DC Bradley, Chem. Rev. 1989, 89, 1317) And [H^OBAKS.Pakswer & R Skoug,in,,Thin dielectric oxide fib made by oxygen assisted pyrolysis of alkoxides,,,The Electrochem.

Soc., Los Angeles, CA, USA, 1970, 619-636) has successfully grown zirconium dioxide and cerium oxide by chemical vapor deposition. However, these mononuclear precursors contain a metal core with an unsaturated 4 coordination number, and the tert_butoxide ligand is decomposed in the presence of traces of water, which is highly sensitive to air or moisture. They are prone to cause a prior reaction in a chemical vapor deposition reactor, and this reaction also leads to a shortening of storage time, especially in the case of chemical vapor deposition using solution injection. [Invention] The object of the present invention is It is a precursor of titanium, wrong and sputum that is provided by the chemical gas. We have found that l_f oxy-mP] is effective in inhibiting the polymerization of the oxygen-suppressing complex and increasing its stability at room temperature. According to the above findings, the present invention provides a titanium, agglomerate, and a ruthenium precursor having a (10) 1 (R 2 ) CH 2 X equation for use in a metal organic chemical vapor deposition process, wherein 1275657 'R is a ruthenium or a ruthenium group, and R 2 is A selectively replaceable alkyl group, the fluorene selected from the group consisting of 〇R and NR2, and R is an alkyl group or a substituted alkyl group. According to a first preferred embodiment of the present invention, the precursor of the chemical vapor deposition method has the following equation : mclxcocr^r^^x]^ where Μ is a metal selected from the group consisting of titanium '鍅 and 铪, l is a ligand, and X is the number of 〇~3', R, R and X are as defined above. The ligand L to be used is an alkoxy group having 1 to 4 carbon atoms, and f is most favored by tertiaiy-butoxide (OBu1), and others such as iso_prop〇xide (〇Pri) can also be used. Equation 0CR1 ( A preferred ligand for the technique in R2) CH2X is μ曱oxy-2-methyl-2-propanolate (mmp). However, other alkoxylate ligands which can be reacted can also be inhibited in the use of the present invention. The functions and functions required for the polymerization of titanium, ruthenium and decane oxides; these other alkoxylate ligands which can be reacted include 〇CH(Me)CH2〇Me OCEt2CH2OMe5 OCH(But)CH2OEt? OC(Bvl)2CH2〇^ φ OCpr^CHaOEt, 0 邮 。. 氏2, 〇.州仰^ OCXButXCHzOPr%, but is not limited thereto. The present invention further provides metal organic chemical vapor phase The precursor of titanium, zirconium and hafnium in the deposition method, which comprises reacting mmpH with a corresponding metal oxide or metal alkylamine in an appropriate molar ratio. This new alkoxy complex, ΖΓ(ΟΒιή2(ιηιηρ;) 2, Ζι·(;ιηιηρ;) 4, HfKOBJMmmph and Hf(mmp)4, which can be synthesized by adding a suitable molar ratio of leg yang to Zr (OBU% and HfiOBV) 4. These complexes have suitable for use in 1275657 Metallic organic chemical vapor deposition required high vapor pressure, and recorded & (called compounds, more difficult to react with air, moisture, and R is - silk, making them in metal organic chemical vapor deposition It is easier to handle and use. The reason why these new (Zr) and 铪_complexes have low air sensitivity is high moisture sensitivity in [ZitOBu%] and [HfiOBu%] (1) If the butoxy group is replaced by the mmp complex, it is less prone to hydrolysis. Moreover, by increasing the coordination number of the central atomic enthalpy (Zr) and hydrazine (Hf), the hydrolysis can be more inhibited. According to the second preferred embodiment of the present invention, it can be extended to other large atomic bands and high positive electricity. For example, 镧La, which has the following equation:

LafOCR^R^^XJs wherein R1 is an anthracene or an alkyl group, and R2 is an alkyl group which is optionally substituted, and is selected from OR and NR2'R is a burnt group or a substituted burnt group. Although other alkoxy ligands available for reaction can also be used... these include OCH(Me)CH2OMe? OCEt2CH2OMe? OCHCBu^^OEt, OCCBu^^OEt, OCCPr^^OEt, OCH(But)CH2NEt2? 肇OC( Pri) 2CH2〇C2H4〇Me and ΟΟχΒι^χα^ΟΡι·1)2, but are not limited thereto. However, it is preferred that the ligand used is 1-methoxy-2-methyl-2-propanolate [OCMe2CH2OMe]. According to a second preferred embodiment, the present invention also provides a preferred method of producing a precursor comprising reacting mmpH with La{N(SiMe3)2;h in an appropriate molar ratio. Using the precursor of the present invention, a single or mixed oxide layer or film can be obtained by conventional metal organic chemical vapor deposition by placing the precursor in a metal organic bubbler or injecting metal organic chemical gas into the liquid. The phase deposition method dissolves the precursor into the appropriate 1275657 inert organic ray, and the other chemical vapor deposition method, such as atomic layer deposition (ALD), by the invention. A film of the wrong, antimony and titanium oxide is obtained. The precursor of the invention can obtain thieves of dioxins, dioxygenation, titania and bismuth dioxide by metal organic chemical vapor deposition; and can also use mixed precursors to obtain oxidation and oxidation. A composite film of cerium oxide, such as zs 〇, brain and tender 〇 氧 氧 与 与 与 与 与 与 与 与 与 与 与 与 与 与 与 与 与 与 与 与 与 与 与 与 与 与 与 与 与 与 与 与 与 与 与 与 与 与 与A mixture of mmp)2 or Bi(mmp)3/Ti(mmp)4 obtained a bismuth-titanate composite film. [Embodiment] The present invention can be further described with reference to the accompanying drawings; the first figure shows the imaginary structure of Μ(ΟΒι%%(πιιηρ) 2 (M=Zr or Hi). The first figure shows Zr(mmp)4 and Hf (mmp) 4 has a similar structure. The third figure shows the laser Raman spectrum of Zr〇2 and Hf〇2 films grown by liquid metal organic chemical vapor deposition using ZifOBi^minph or HfiOBu^minph. The invention is further described by the following examples. Example 1 Preparation of ΟΒ (ΟΒιι) 2 (ιηιηρ) 2 2.8 ml (2.69 g, XO mmol) of ZrCOBu) 4 was dissolved in hexane (ca. 4 〇 ml), Then mmpH (1.6 ml, 1.44 g, 13.9 mmol) was gradually added dropwise, and the mixture was heated to cause a countercurrent, and stirring was continued for 2 hours, followed by cooling to room temperature, and the pressure was reduced by I275657. The lower volatiles will evaporate, and the white crystalline solid can be further precipitated from the sinter. Melting point: 96-101 ° C (uncorrected) Minor analysis · Calculated value C : 48.71%, Η : 9.10% Actual value C : 46.32%, Η : 8.77% 4 NMR : (400MHz, d8_tol) 1.19 (s, 12Η , OC(CH3)2CH2OCH3), 1.37(s,18H,OC(CH3)3), 3.23(s,4H,OC(CH3)2Cg2〇CH3),3·40 (s,6H, · OC(CH3)2CH2OCii3 ). 13CNMR: 34.1 (OC(£H3)2CH2OCH3), 38.5 (OC(£H3)3), 65.4 (OC(CH3)2CH2C^H3), 78.6 (OQCH3)2CH2OCH3 and 〇C(CH3)3)? 90.5 (OC (CH3)2CH2OCH3) 〇IR : (u cm·1,Nujol,NaCl)3588(w), 3422(w), 2725(w), 2360(w),1356(s),1277(m),1227( m), 1206(8), 1177 (8), 1115(s), 1080(8), 1012(s), 974(s), · 936(s), 801 (8), 782(8), 595(s). The imaginary structure of Ζι^ΟΒι^ΜππηρΚ The first picture shows. Case 2

Preparation of Zr(mmp)4 2.0 g (5.2 mmol) of Zi^OPr%· PrOH was dissolved in hexane (ca. 40 ml), and then mmpH (2.6 ml, 2.35 g, 22.5 mmol) was gradually added dropwise. The mixture is heated to produce a countercurrent, and the mixture is continuously stirred for 2 hours, and then allowed to cool to room temperature. When the pressure is reduced, the volatiles are evaporated to obtain a white viscous oil which is the product (output 10 1275657 rate: 2.4g, 94%).

Zr(mmp)4 can also be synthesized from the Zr(NR2)4 complex, such as: gradually adding mmpH (6.9g, 65.8mmol) into [Zr(NEt2)4] mixed with hexane (50cm3) ( 5 〇g, 13 2mm〇1) solution. This mixture was boiled for 2 hours in the case of a countercurrent, and then cooled to room temperature, and the volatile product was discharged by vacuum to give the product (yield: 6.25 g, 94%). Microanalysis: Calculated C: 47.67%, Η: 8.82% Actual C: 47.80%, Η: 8.79% 4 NMR: (400MHz, d8-tol): 1.21 (s, OC(CH3)2CH2OCH3), _ 3.16 ( s, OC(CH3)2CH2〇CH3) 3.27(s, OC(CH3)2CH2OCii3). 13CNMR: (l〇〇MHz, d8-tol): 32.1 (OC(£H3)2CH2OCH3), 64.8 (OC(CH3)2CH2O£H3), 76.0 (C^(CH3)2CH2OCH3), 88.5 (OC (CH3) £H2OCH3). IR : (y cm·1,Nujol,NaCl)3589(w),3448(w,br), 2724(m),2346(w),1377(s),1322(m),1279(m), 馨1239(m), 1176(s), 1134(m), 1114(s), 1081(m)5 1018(8),996(m),982(8),958(m),937(m), 917(m),845 (m), 804(m), 784(m), 594(8). Example 3

Hf(OBu)2(mmp)2 3.5 ml (4.0 g, 8.5 mmol) of HfifOBu% was dissolved in hexane (40 ml) to form a yellow liquid, then mmpH (2.0 ml, 1.79 g, 19.0 mmol) was gradually added dropwise. The mixture is heated to produce a countercurrent, and the mixture is continuously stirred for 2 hours, and then allowed to cool to room temperature. Under the pressure of 11 1275657, the volatile matter evaporates and the white crystalline solid can be evaporated from the The alkane was precipitated again, which was the crude product (yield: 4.4 g, 97%). Melting point: 100-104 ° C (uncorrected) Microanalysis: Calculated value C: 40.71%, Η: 7.61% Actual value C: 38.93%, Η: 7.30% hNMR : (400MHz, d8-tol) : (5=1.18 (s, 12H, OC(CH3)2CH2 OCH3), 1 · 3 8 (s, 18H, OC(CH3)3), 3.21 (s512H9OC(CH3)2CH2〇CH3)5 · 3.42(s,12H,OC(CH3) 2CH2OQi3). 13C NMR: (100 MHz d8-tol): 5 = 34.4 (OC(QH3)2CH2OCH3 I 38.6(OC(CH3)3)9 65.7 (〇C(CH3)2CH2OCH3)5 78.0, 79.1 (OC( CH3)2 £H2OCH3 and 0£(CH3)3), 90.9(OC(CH3)2QHpCH3). IR · (υ cm'1,Nujol,NaCl) : 3441(w)52726(m)5 2256(w), 1272(8), 1177(S), 1O74(S), 1O16(S), 976(S), 8O2(S), 782(S), 0 593(s).

The imaginary structure of Hf(OBut)2(mmp)2 is as shown in the first figure. Example 4

Preparation of Hf(mmp)4 4.0 ml (5.56 g, 11.9 mmol) of [Hf(NEt2)4] was dissolved in hexane (6 〇ml), then Hmmp (7.0 ml, 6.3 g, 60 mmol) was gradually added dropwise The mixture was heated to give a countercurrent and continued to be disturbed for 90 minutes, then allowed to cool to room temperature, and the volatiles were discharged by vacuum, leaving a white viscous oil as the product (yield: 6.88g, 97.5%) 12 1275657 Microanalysis: Calculated C: 40.63%, Η: 7.52% Actual C: 39.85%, Η: 7·32% lR NMR: 1.30 (s, 24H, OC(CH3)2CH2OCH3) , 3.28 (s, 8H, OC(CH3)2C^OCH3), 3·36 (s, 12H, OC(CH3)2CH2OC^3). 13C NMR: 34.74 (OC(〇I3)2CH2OCH3), 65.16 (OC(CH3)2 CH2O^H3), 79.83 (OQCH3)2CH2OCH3), 90.25 (OC(CH3)2^H2OCH3). Repair IR: (Nujol/ NaCl): 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).

The imaginary structure of Hf(mmp)4 is as shown in the second figure. Example 5 Preparation of ZKOPPHmmph · Take 1.068 (2.75111111〇1) of 21' (0?1^)4.?1^011 dissolved in hexane ((^4〇1111), then 1_ 曱oxy-2-曱Base-2_propanol [mmpH] (0.65 ml, 0.57 g, 5.5 mmol) was gradually added dropwise, and the mixture was heated to give a countercurrent, and stirring was continued for 2 hours, followed by cooling to room temperature, in the case of a decrease in pressure. Next, the volatiles will evaporate, leaving the viscous oil as the product. Microanalysis: Calculated value C: 46.23%, Η: 8.73% Actual value C: 44.17%, Η: 8.47% ^ NMR : ( 400MHz? d8-tol): 1.26(s?OC(CH3)2 CH20CH3), 13 1275657 1.32(d,OCH(CH3)2), 3.26(2, OC(C)2CH2OCH3), 3.36 (s, OC( CH3) 2CH2OC mutual 3), 4.46 (m, OCSCH3) 2). 13CNMR: (100MHz, d8-tol): 32.1(OC(£//3)2CH2OCH3), 34.2 (OCH(£H3)2), 64.9 (OC(CH3)2CH20〇I3), 76.1,76.4 (O^H (CH3)2 and 0£(CH3)2CH20CH3), 88.6(OC(CH3)2^2〇CH3). IR : (υ cm-1, Nujol, NaCl) 3589(w), 3423(w), 2724(w), 2282(w), 1239(w), 1175(m), 1115(m), 1019(m) ), 959(m). . Example 6

Preparation of TiipPrMmmp)) mmpH (2.81 g, 27 mmol) was gradually dropped into a solution of 己烷ί (ΟΡ4 (3.84 g, 13.5 mmol) dissolved in hexane (20 ml). This mixture was boiled for 90 minutes in the case of countercurrent, followed by After cooling, the volatiles are discharged by vacuum to obtain the product as a colorless oil. Microanalysis: TiC16H3604 Calculated value C: 51.61%, Η: 9.75% | Experimental value C: 51.20%, Η: 9.92% 1Β^ΜΚ( 06Ό50Ό3άϊ30°〇δ U(26H5d?(C^3)2CH; CHsOCHKCShC); δ 3·2(10Η, 2 singlets, CH3OC凼(CH3)2C); δ 4·5(2Η, m,(CH3)2C® · l3C{lR} NMR (C6D5CD35 30°C): 32(OC(ai3)2CH2OCH3)? 33.4(OCH(CH3)2)5 64.4(OC(CH3)2CH2OCH3)? 81.7(OC(CH3)2CH2〇CH3 86.5 (OCH(CH3)2)? 88(OC(CH3)2GH2OCH3). 1275657 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 gradually added dropwise to a pale brown solution of Ti(NEt2)4 (2.85 g, 3 ml; 8.47 mmol) dissolved in hexane (20 ml). This mixture was boiled for 1.5 hours in the case of a countercurrent, and then allowed to cool, and the volatiles were discharged by a vacuum to obtain a product (Ti (mmp) 4 as a pale brown oil. < Microanalysis: TiC2〇H44〇8 Calculated value C: 52.17%, Η: 9.63% Experimental value C: 51.95%, Η: 9.97% 'Η NMR (C6D5CD3 at 30°C) 5 1.3(24H5s5CH3OCH2 (CH3)2 C); δ 3·2 (20Η, 2 singlets, C7/3OQ^2(CH3)2C); VT 4 NMR shows a steep and distinct peak from _50°C to +50°C, no width is very clear of. l3C{lR}mAR(C6O5CO3, 30°〇: 31.9(00(αί3)2〇Η2ΟΟΗ3)5 | 64.5(OC(CH3)2CH2O^H3), 81.7(0£(CH3)2CH20CH3), 87(OC(CH3) 2£H2OCH3). IR (Nujol, cm·1) 2975s, 2931s, 2876s, 2829m, 2625w, 1461m, 1360s, 1331m, 1277m, 12406m, 1116s, 1004s, 850m·, 796s, 775s, 625s.

Preparation of La(mmp)3 2.89 g (4.6 mmol) of La{N(SiMe3)2}3 was dissolved in toluene (50 ml), then mmpH (2.2 ml, 1.96 g, 18.7 mmol) was gradually added to the chamber. The temperature continued to disturb 21 15 1275657 hours, and _ vacuum shifted the hairpin, leaving the brown lion as the product (yield: 1.8g, 87% vs. 镧). Microanalysis: LaC15H33〇6 Calculated value C: 40.18%, η: 7.43% Actual value C: 40.01%, η: 7.38% Example 9 from ZitOBu^mmph, Zr(mmp)4, Ηί(〇Βχι%(ππηρ)2 and

Hf(mmp)4 deposits cerium oxide and cerium oxide. These four compounds are excellent precursors for the deposition of zirconium dioxide and dioxide to metal films by metal organic chemical vapor deposition. The following table—the zirconium dioxide and cerium oxide films produced by the same general conditions for the 丨 丨 chemical vapor deposition method. Table 1 is one of ΖΓ(ΟΒι4(ιηιηρ)2,ΖΓ(πιιηρ)4,Ηί(ΟΒιι%(πιπιρ)2 or

Hf(mmp)4 is a precursor, and growth conditions of zirconium dioxide and ruthenium dioxide films are grown by liquid injection chemical vapor deposition. Substrate temperature 350-650 ° C Reactor pressure 20-30 mbar Precursor solution concentration 0.1M in the reaction rate of the benzene benzene precursor solution 4-8 cm3 hr"1 Evaporator J31I temperature 130-150 〇C gas carrier flow rate 400 -600 cn^min·1 Oxygen flow rate 100-150 cm3min-1 16 1275657 Substrate oxide growth rate

The meaning of (4) Raman can be determined to be cerium oxide or cerium oxide; the second figure shows the spectrum of the dioxide and the dioxide which are grown from Zr(0But)2(mm or Η'ΛΟηπιρ)2; Yes, most of these films belong to the alpha or monoclinic system. [Simple description of the diagram] · The first figure shows the imaginary structure of ΒρΒι^ιηιηρ)2 (M=Zr or Hf). The first figure shows that Zr(mmp)4 has a similar structure to Hf(mmp)4. The third graph shows the Raman spectra of Ζι〇2 and Excited 2 films grown using Zr(OBut)2(mmp)24 Hf(〇But)2 body-exposed metal. [Main component symbol description] 17

Claims (1)

1275 furnace • fc X. Patent application scope: 1. A precursor used in metal organic chemical vapor deposition, which has the following formula: M(L)2[〇CR1(R2)CH2X]2 where μ is selected From titanium, ruthenium and a given metal, [is a burnt oxygen ligand containing one carbon atom 2, R1 is η or - a burnt group containing 4 carbon atoms, R疋1 can be selectively replaced and An alkyl group having from 丨4 to 4 carbon atoms, the oxime selected from OR, wherein R is a filament or an alkyl group which may be substituted and contains 4 carbon atoms. 2. The precursor of claim 1, wherein the ligand 1 is selected from the group consisting of tertiary-butoxide and iso-propoxide. 3. The precursor described in claim 1 or 2, wherein the ligand of the formula OCRkR^a^X is 1-decyloxy_2_methyl_2_pr〇pan〇late 〇4 · The precursor as described in claim 1, wherein the ligand of the formula OCR^R^CHsX is selected from the group consisting of 〇CH(Me)CH2〇Me, OCEt2CH2OMe, OCH^i^CI^OEt, OC ^Bi^CH^OEt, OCXPi^Ci^OEt. 5. The precursor described in the first paragraph of the patent application, the general formula is Zi^OBu^mmph 〇6. The precursor described in the first paragraph of the patent application, the general formula is Hf^OBu^mmp )〗. 7. The precursor as described in claim 1 of the patent application, especially the method for producing titanium, tantalum and niobium precursors by metal organic chemical vapor deposition, comprising 18 1275657 HOCR^R^Ci^X The corresponding metal oxide is reacted in an appropriate molar ratio, wherein R1 is hydrogen or an alkyl group having 1 to 4 carbon atoms, and R2 is an alkyl group which is optionally substituted and contains 1 to 4 carbon atoms, X Is 〇R, wherein R is an alkyl group or an alkyl group which may be substituted and contains 丨~4 carbon atoms. 8. A precursor for use in metal organic chemical vapor deposition, having the following formula: La[OCR1(R2)CH2X]3 wherein R1 is hydrazine or an alkyl group, and r2 is a selective Substituted alkulylene, X is selected from the group consisting of OR and NR2, wherein R is an alkyl group or an alkyl group which may be substituted. 9. The precursor as described in claim 8 of the claim, wherein the ligand is ^曱oxy-2·methyl-2-propanolate [OCMe2CH2OMe]. 10. The precursor as described in claim 8 wherein the ligand is selected from the group consisting of 〇CH(Me)CH2OMe, OCEt2CH2OMe, OCH(But)CH2OEt?OC(But)2CH2OEt?〇C(Pri)2CH2OEt? OCH (But) CH2NEt25 OCXPr^CI^OQHUOMe and ΟΟχΒι^χΟΗ^ΟΡΓ%·11· A precursor of chemical vapor deposition, which has the general formula La[mmp]3. 12. The precursor of claim 8, wherein the method of improving the precursor comprises: reacting HOCf^RbCH^X with La{N(SiMe3)2}3 in an appropriate molar ratio. 13. The precursor as described in claim 1 or 8 or item η, which specifically provides an improvement in the precursor of a chemical vapor deposition process, wherein at least one of the improvements is preceded by the use of conventional metal organic chemistry. Vapor deposition method for depositing a single or mixed oxygen 19 1275657 layer or film, wherein the precursor is placed in a metal organic bubbler; or using a liquid-ejected metal organic chemical vapor deposition method, single or mixed The oxide layer or film is deposited wherein the precursor is first dissolved in a suitable inert organic solvent and then vaporized using a heated gasification unit. 20 1275657 VII. Designated representative map: (1) The representative representative of the case is: None. (2) A brief description of the symbol of the representative figure: 8. If there is a chemical formula in this case, please disclose the chemical formula that best shows the characteristics of the invention: