CN1732286A - Deposition processes using group 8 (VIII) metallocene precursors - Google Patents

Abstract

Disclosed herein is a process for producing a film, coating or powder employing a metallocene or metallocene-like precursor having the general formula CpMCp', where M is a metal selected from the group consisting of Ru, Os and Fe; Cp is a first substituted cyclopentadienyl or cyclopentadienyl-like, e.g., indenyl, moiety that includes at least one substituent group D1, where D1 is X; Ca1Hb1Xc1; Ca2Hb2Xc2(C=0)Ca1Hb1Xc1; Ca2Hb2Xc2OCa1Hb1Xc1; Ca2Hb2Xc2(C=0)OCa1Hb1Xc1; or Ca2Hb2Xc2O(C=0)Ca1Hb1Xc1; and Cp' is a second substituted cyclopentadienyl or cyclopentadienyl-like, e.g., indenyl, moiety that includes at least one substituent group D1', where D1' is X; Ca1Hb1Xc1; Ca2Hb2Xc2(C=0)Ca1Hb1Xc1; Ca2Hb2Xc2OCa1Hb1Xc1; Ca2Hb2Xc2(C=0)OCa1Hb1Xc1; or Ca2Hb2Xc2O(C=0)Ca1Hb1Xc1. D1 and D1' are different from one another. X is a halogen atom or NO2; a1 is an integer between 1 to 8; b1 is an integer between 0 and 2(a1)+1-c1; c1 is an integer between 0 and 2(a1)+1 -b1; b1 + c1 is at least 1; a2 is an integer between 0 and 8; b2 is an integer between 0 and 2(a2) + 1 - c2; andc2 is an integer between 0 and 2(a2) + 1 - b2. The process can be used in manufacturing or processing electronic devices.

Description

Use the deposition process of 8 families (VIII) metallocene precursors

Background of invention

Chemical vapour deposition (CVD) (CVD) method is applied in semiconductor manufacturing or the processing, and for example wafer or other surface form material membrane in substrate. In CVD, cvd precursor (also claiming the CVD compound) is to be decomposed to form the film with required composition by heating power, chemistry, photochemistry or the method by excitation of plasma. For example the gaseous state cvd precursor can with the substrate contact that is heated to temperature and is higher than the decomposition temperature of described precursor, to form metal or metal oxide film in substrate.

Contain ruthenium (Ru), ruthenium-oxide (RuO₂) or the film of iron (Fe) have good electric conductivity and very high work function and chemistry and heat endurance, tolerance interlayer chemical species diffusion is also compatible with multiple dielectric base material. For example Ru and RuO₂The studied membrane electrode material as semiconductor devices such as DRAM (dynamic RAM) device of film.

Utilizing the example of the film of ruthenium based precursor preparation to see is set forth in: the U.S. Patent number 6,440,495 that was issued to Wade etc. on August 27th, 2002; Be issued to the U.S. Patent number 6,074,945 of Vaartstra etc. on June 13rd, 2000; J.Peck etc. in the U.S. Patent Application Publication 2002/0102826 of the manufacture method that disclosed autograph is semiconductor integrated circuit on August 1st, 2002; The 201st the electrochemical society meeting special meeting collection of thesis Proceedings of the Symposium that holds in Philadelphia, Rapod Thermal and other Short-Time Processing Technologies III, Electronics, Dielectroc Scienece and Technology, and High Temperature Materia Division, the 2002-11 volume, the 235-242 page or leaf is entitled as Chemical Vapor Deposition of Novel Precursors for Advanced Capacitor Electrodes (being used for the chemical vapour deposition (CVD) of the novel precursor of senior capacitance electrode). Above-mentioned patent, disclosed patent application and meeting report paper are attached to herein by reference.

Two (pentahapto cyclopentadienyl groups) close ruthenium (ruthenocene) and symmetrical diethyl, and to replace ruthenocene (1,1 '-diethyl ruthenocene) studied as utilizing the CVD technology to form the possible precursor of ruthenium base film.

These compounds are by several synthetic route preparations.

For the preparation of a kind of known method of ruthenocene shown in Figure 1A, by RuCl₃·XH ₂O and cyclopentadiene react in the presence of Zn and generate ruthenocene, ZnCl₂And HCl. Figure 1B shown a kind of similar approach that adopts the ethyl substituted-cyclopentadienyl prepare 1,1 '-the diethyl ruthenocene. Usually the productive rate of this method is about 70%.

Shown in Fig. 1 C, do not replace ruthenocene and can pass through cyclopentadiene yet, chlorine (cyclopentadienyl group) two (triphenylphosphines) closes ruthenium (II) and sodium hydride (NaH) and reacts in benzene and prepare. Chlorine (cyclopentadienyl group) two (triphenylphosphines) closes ruthenium (II) precursor and reacts in ethanol by ruthenium trichloride and triphenylphosphine and synthesize.

The method of the another kind of synthetic ruthenocene of having studied comprises that two (alkyl cyclopentadienyl) closes iron compound and RuCl₃·XH ₂The metal transfer reaction of O, the result generates 1,1 ' dialkyl group ruthenocene and ferric trichloride (FeCl with low-yield₃), and very difficult separating ferrum class material.

Single replace ruthenocene such as 1-ethyl ruthenocene be as 1,1 '-impurity in the diethyl ruthenocene building-up process and generating. It is mixture heating by will two (cyclopentadienyl group) closing ruthenium, aluminium chloride and polyphosphoric acid that the another kind of single ruthenocene that replaces, the tert-butyl group (cyclopentadienyl group) (cyclopentadienyl group) close ruthenium, then with tert-butyl alcohol reaction and distill subsequently and prepare.

In general, above-mentioned synthetic method is often followed low-yield, competitive dimerization reaction, complicated product separation, and the specially treated technology of hazardous agents such as NaH. In addition, as shown in Figure 1A and 1B, two cyclopentadienyl rings of these synthetic methods one step additions, therefore be suitable for preparing do not replace ruthenocene or symmetrical replace 1,1 '-the diethyl ruthenocene. Ruthenocene and 1,1 '-vapour pressure of diethyl ruthenocene all relatively low (under 100 ℃ less than 10 holders). Under the room temperature ruthenocene be solid and 1,1 '-the diethyl ruthenocene is liquid.

The usually preferred stronger cvd precursor of volatility for example is the precursor of liquid rather than solid under the room temperature. Desirable cvd precursor also is thermal decomposition and can generates uniform film under suitable CVD condition in addition.

Therefore need to continue research ruthenium base cvd precursor and new membrane deposition process. Also need the research preparation to contain the method for the film of ruthenium or other 8 family (VIII) metals.

Summary of the invention

The present invention relates generally to the deposition process of preparation example such as the materials such as film, coating or powder, and described material contains 8 families (VIII) metal and/or 8 families (VIII) metal oxide. Described method comprises decomposes at least a Asymmetrical substitute metallocene precursors to generate described material. The Asymmetrical substitute metallocene precursors represents that with general formula CpMCp ' wherein M is for being selected from the metal of ruthenium (Ru), osmium (Os) and iron (Fe); Cp is first substituted cyclopentadienyl group or cyclopentadiene base class (for example indenyl) part, and this part comprises at least one substituent group D₁ Cp ' is second substituted cyclopentadienyl group or cyclopentadiene base class (for example indenyl) part, and this part comprises at least one substituent group D₁′；D ₁And D₁' two groups differ from one another and independently are selected from:

X；

C _a1H _b1X _c1；

C _a2H _b2X _c2(C＝O)C _a1H _b1X _c1；

C _a2H _b2X _c2OC _a1H _b1X _c1；

C _a2H _b2X _c2(C＝O)OC _a1H _b1X _c1 And

C _a2H _b2X _c2O(C＝O)C _a1H _b1X _c1；

Wherein

X is halogen atom or nitro (NO₂)；

A1 is 1 to 8 integer;

B1 is the integer of 0 to 2 (a1)+1-c1;

C1 is the integer of 0 to 2 (a1)+1-b1;

B1+c1 is at least 1;

A2 is 0 to 8 integer;

B2 is the integer of 0 to 2 (a2)+1-c2;

C2 is the integer of 0 to 2 (a2)+1-b2;

In one embodiment, the present invention relates to for the method that deposits masking. Described method comprises the steam decomposition step of asymmetric metallocene or class of metallocenes compound, wherein decomposition is to realize by heat, chemistry, photochemistry or excitation of plasma, the general formula of metallocene or class of metallocenes compound is aforesaid CpMCp ', forms film in substrate thus.

In preferred embodiments, D₁For:

X；

C _a1H _b1X _c1；

C _a2H _b2X _c2(C＝O)C _a1H _b1X _c1；

C _a2H _b2X _c2OC _a1H _b1X _c1；

C _a2H _b2X _c2(C＝O)OC _a1H _b1X _c1 Perhaps

C _a2H _b2X _c2O(C＝O)C _a1H _b1X _c1；

Wherein

X is fluorine (F), chlorine (Cl) bromine (Br), iodine (I) or NO₂；

A1 is 2 to 8 integer;

B1 is the integer of 0 to 2 (a1)+1-c1;

C1 is the integer of 0 to 2 (a1)+1-b1;

B1+c1 is at least 1;

A2 is 0 to 8 integer;

B2 is the integer of 0 to 2 (a2)+1-c2;

C2 is the integer of 0 to 2 (a2)+1-b2, and

D ₁' be:

X；

C _a1H _b1X _c1；

C _a2H _b2X _c2(C＝O)C _a1H _b1X _c1；

C _a2H _b2X _c2OC _a1H _b1X _c1；

C _a2H _b2X _c2(C＝O)OC _a1H _b1X _c1 Perhaps

C _a2H _b2X _c2O(C＝O)C _a1H _b1X _c1；

Wherein

X is F, Cl, Br, I or NO₂；

A1 is 1 to 8 integer;

B1 is the integer of 0 to 2 (a1)+1-c1;

C1 is the integer of 0 to 2 (a1)+1-b1;

B1+c1 is at least 1;

A2 is 0 to 8 integer;

B2 is the integer of 0 to 2 (a2)+1-c2;

C2 is the integer of 0 to 2 (a2)+1-b2;

An instantiation of Metallocenic compound that the inventive method is used is the 1-methyl, 1 '-the ethyl ruthenocene.

At least one can comprise one or more other substituting group such as D among Cp or the Cp '₂、D ₃、D ₄、D ₅、D ₂′、D ₃′、D ₄' and D₅′。

Above-claimed cpd is for passing through the standby Ru-of CVD legal system, and the existing method of Os-or Fe-base film provides extra selection and flexibility. For example some this compounds at room temperature has higher vapour pressure for liquid and than traditional precursor. Find in addition for example 1-methyl, 1 '-vapour pressure of ethyl ruthenocene is higher than 1,1 '-the diethyl ruthenocene. Higher vapour pressure is brought many economic advantages, and for example productivity ratio improves and the film production cost. The functionalization of cyclopentadienyl rings has changed many character by the modification of cyclopentadienyl rings in the compounds of this invention, such as solubility, vapour pressure, decomposability, flammability and other response path, reducing/oxidizing electromotive force, geometric configuration, preferred orientation and electron density distribution. Therefore

The present invention has several advantages. The compounds of this invention is for passing through the standby Ru-of CVD legal system, and the existing method of Os-or Fe-base film provides extra selection and flexibility. Some this compounds at room temperature is liquid. Find in addition the 1-methyl isophthalic acid '-vapour pressure of ethyl ruthenocene is higher than 1,1 '-the diethyl ruthenocene. The standalone feature of each cyclopentadienyl rings has changed many character such as solubility, vapour pressure, decomposability, flammability and other response path, reducing/oxidizing electromotive force, geometric configuration, preferred orientation and electron density distribution by the modification of cyclopentadienyl rings in the compounds of this invention. The functionalization permission of cyclopentadienyl rings is made amendment to metallocene or is optimized to be fit to required application.

The accompanying drawing summary

Figure 1A describes the synthetic route that a preparation does not replace the prior art of ruthenocene.

Figure 1B describe a preparation 1,1 '-synthetic route of the prior art of diethyl ruthenocene.

Fig. 1 C describes the synthetic method that another kind of preparation does not replace the prior art of ruthenocene.

Fig. 2 A shows the metallocene molecular formula of staggered conformation.

Fig. 2 B shows the metallocene molecular formula of eclipsed conformation.

Fig. 3 shows that the present invention two replaces the structural formula of asymmetric Metallocenic compound.

Fig. 8 is for describing the sketch of thin film deposition system, and described system can be used for carrying out an embodiment of the inventive method.

Fig. 9 is the sketch of equipment, and described equipment can be used for depositing to carry out the film chemical steam at a gas mix manifold containing gasified liquid or solid precursor.

Figure 10 is the sketch of thin film deposition reactor, and described reactor can be used for implementing one embodiment of the invention.

Figure 11 and 12 is scanning electron microscopy, shows the cross-sectional image of the ruthenium film that the inventive method is prepared.

Figure 13 is for utilizing the inventive method at SiO₂The energy-dispersive spectroscopy of the ruthenium film for preparing in/Si the substrate.

Figure 14 is for utilizing the 1-methyl, 1 '-film of ethyl ruthenocene precursor deposition and utilize 1,1 '-the meter surface resistance of the film of diethyl ruthenocene deposition and the function relation figure between the carburettor temperature.

Figure 15 is for utilizing the 1-methyl, 1 '-thickness of the film of ethyl ruthenocene precursor deposition with utilize 1,1 '-film of diethyl ruthenocene deposition compare and carburettor temperature between function relation figure.

Figure 16 is for utilizing the 1-methyl, 1 '-ethyl ruthenocene precursor and 1,1 '-resistivity of the film of diethyl ruthenocene deposition and the function relation figure between the carburettor temperature.

Detailed Description Of The Invention

Above-mentioned and other target of the present invention, feature and advantage will clearly be manifested in to the more detailed description of the preferred embodiment of the invention (as shown in drawings) following, and identical part adopts same Reference numeral in different accompanying drawings. Accompanying drawing not necessarily proportionally focuses on setting forth principle of the present invention.

The present invention relates generally to the method for the preparation of film, coating or powder. Described method comprises the step of 8 families (VIII) Metallocenic compound of the following at least a Asymmetrical substitute of decomposition that will further set forth. This place uses term " metallocene " to refer to Organometallic complexes, sandwich type structure with similar ferrocene, think that wherein transition metal and η n coordination ring close (electronics moves), described η with the π bond in the track that extends the ring above and belowⁿThe coordination ring is generally the aromatic ring part, Cp and Cp ', and wherein n refers to the carbon atom number with the loop section of transition metal bonding.

In preferred embodiments, Cp and Cp ' all independently are selected from cyclopentadiene or indenyl (phenyl that condenses and cyclopentadiene ring). If all carbon atoms of cyclopentadiene ring all participate in the bonding with transition metal, then these parts are called η⁵Coordination. Thereby the complete description of ferrocene will be (η⁵-C ₅H ₅) ₂Fe。

Fig. 2 A is depicted as the staggered conformation of metallocene, and wherein M is 8 families (VIII) metals, for example ruthenium, osmium or iron. Metallocene also can have the eclipsed conformation shown in Fig. 2 B. Molecular formula used herein is not to describe the concrete conformation of metallocene.

The η except cyclopentadienyl group hereinⁿCoordination partly is called as " cyclopentadiene base class ". This area is well-known, can exist other counter ion counterionsl gegenions group with balancing charge and formation neutral molecule in this compounds.

The used Metallocenic compound general formula of the inventive method is CpMCp ', and wherein M is Ru, Os or Fe, and Cp and Cp ' are cyclopentadienyl group or cyclopentadiene base class, for example indenyl part. Cp and Cp ' are substituted separately and Cp and Cp ' differ from one another.

More particularly, at least one hydrogen (H) atom is substituted base such as D in each Cp and Cp ' part₁And D₁' institute is displacement respectively.

D ₁And D₁' differ from one another and independently be selected from:

X；

C _a1H _b1X _c1；

C _a2H _b2X _c2(C＝O)C _a1H _b1X _c1；

C _a2H _b2X _c2OC _a1H _b1X _c1；

C _a2H _b2X _c2(C＝O)OC _a1H _b1X _c1 And

C _a2H _b2X _c2O(C＝O)C _a1H _b1X _c1；

Wherein

X is halogen atom or nitro (NO₂)；

A1 is 1 to 8 integer;

B1 is the integer of 0 to 2 (a1)+1-c1;

C1 is the integer of 0 to 2 (a1)+1-b1;

B1+c1 is at least 1;

A2 is 0 to 8 integer;

B2 is the integer of 0 to 2 (a2)+1-c2;

C2 is the integer of 0 to 2 (a2)+1-b2;

This place uses the codomain of integer to comprise the border. Can use straight chain or side chain substituent group D₁And D₁'. D for example₁And/or D₁' can be straight chain or side chain C1-C8 alkyl.

In one embodiment of the invention, D₁For:

X；

C _a1H _b1X _c1；

C _a2H _b2X _c2(C＝O)C _a1H _b1X _c1；

C _a2H _b2X _c2O C _a1H _b1X _c1；

C _a2H _b2X _c2(C＝O)OC _a1H _b1X _c1 And

C _a2H _b2X _c2O(C＝O)C _a1H _b1X _c1；

Wherein

X is halogen atom, such as fluorine (F), chlorine (Cl), bromine (Br) or iodine (I);

A1 is 2 to 8 integer;

B1 is the integer of 0 to 2 (a1)+1-c1;

C1 is the integer of 0 to 2 (a1)+1-b1;

B1+c1 is at least 1;

A2 is 0 to 8 integer;

B2 is the integer of 0 to 2 (a2)+1-c2;

C2 is the integer of 0 to 2 (a2)+1-b2; And

D ₁' be:

X；

C _a1H _b1X _c1；

C _a2H _b2X _c2(C＝O)C _a1H _b1X _c1；

C _a2H _b2X _c2OC _a1H _b1X _c1；

C _a2H _b2X _c2(C＝O)OC _a1H _b1X _c1 And

C _a2H _b2X _c2O(C＝O)C _a1H _b1X _c1；

Wherein

X is halogen atom;

A1 is 1 to 8 integer;

B1 is the integer of 0 to 2 (a1)+1-c1;

C1 is the integer of 0 to 2 (a1)+1-b1;

B1+c1 is at least 1;

A2 is 0 to 8 integer;

B2 is the integer of 0 to 2 (a2)+1-c2;

C2 is the integer of 0 to 2 (a2)+1-b2;

In one embodiment, D₁Be selected from:

C _a1H _b1X _c1；

C _a2H _b2X _c2(C＝O)C _a1H _b1X _c1；

C _a2H _b2X _c2OC _a1H _b1X _c1；

C _a2H _b2X _c2(C＝O)OC _a1H _b1X _c1 Perhaps

C _a2H _b2X _c2O(C＝O)C _a1H _b1X _c1；

Wherein:

X is halogen atom, for example F, Cl, Br or I;

A1 is 1 to 8 integer;

B1 is the integer of 0 to 2 (a1)+1-c1;

C1 is the integer of 0 to 2 (a1)+1-b1;

B1+c1 is equal to, or greater than 1;

A2 is 0 to 8 integer;

B2 is the integer of 0 to 2 (a2)+1-c2;

C2 is the integer of 0 to 2 (a2)+1-b2;

B2+c2 is equal to, or greater than 1;

And D₁' be selected from:

C _a1H _b1X _c1；

C _a2H _b2X _c2(C＝O)C _a1H _b1X _c1；

C _a2H _b2X _c2O C _a1H _b1X _c1；

C _a2H _b2X _c2(C＝O)OC _a1H _b1X _c1；

C _a2H _b2X _c2O(C＝O)C _a1H _b1X _c1；

Wherein

X is halogen atom, for example F, Cl, Br or I;

A1 is 1 to 8 integer;

B1 is the integer of 0 to 2 (a1)+1-c1;

C1 is the integer of 0 to 2 (a1)+1-b1;

B1+c1 is equal to, or greater than 1;

A2 is 0 to 8 integer;

B2 is the integer of 0 to 2 (a2)+1-c2;

C2 is the integer of 0 to 2 (a2)+1-b2;

B2+c2 is equal to, or greater than 1;

In another embodiment, D₁Be halogen atom X (for example F, Cl, Br or I); And D₁' be selected from:

C _a1H _b1X _c1；

C _a2H _b2X _c2(C＝O)C _a1H _b1X _c1；

C _a2H _b2X _c2OC _a1H _b1X _c1；

C _a2H _b2X _c2(C＝O)OC _a1H _b1X _c1；

C _a2H _b2X _c2O(C＝O)C _a1H _b1X _c1；

Wherein

X is halogen atom;

A1 is 2 to 8 integer;

B1 is the integer of 0 to 2 (a1)+1-c1;

C1 is the integer of 0 to 2 (a1)+1-b1;

B1+c1 is equal to, or greater than 1;

A2 is 0 to 8 integer;

B2 is the integer of 0 to 2 (a2)+1-c2;

C2 is the integer of 0 to 2 (a2)+1-b2;

B2+c2 is equal to, or greater than 1;

Figure 3 shows that an example of Metallocenic compound of the present invention (CpMCp ') structural formula.

One of the Cp of metallocene of the present invention or class of metallocenes compound and Cp ' part or both also comprise other substituent group D of optional one or more_x In an example, at least one is polysubstituted cyclopentadiene base or indenyl part among Cp and the Cp '.

Figure 4 shows that the universal architecture formula of Metallocenic compound CpMCp ' of the present invention. D₁And D₁' as mentioned above independent selection. D₂、D ₃、D ₄、D ₅、D ₂′、D ₃′、D ₄' and D₅' independently be selected from:

C _a1H _b1X _c1；

C _a2H _b2X _c2(C＝O)C _a1H _b1X _c1；

C _a2H _b2X _c2OC _a1H _b1X _c1，

C _a2H _b2X _c2(C＝O)OC _a1H _b1X _c1, perhaps

C _a2H _b2X _c2O(C＝O)C _a1H _b1X _c1

Wherein,

A1 is 0 to 8 integer

B1 is the integer of 0 to 2 (a1)+1-c1

C1 is the integer of 0 to 2 (a1)+1-b1

B1+c1 is equal to, or greater than 1

A2 is 0 to 8 integer

B2 is the integer of 0 to 2 (a2)+1-c2

C2 is the integer of 0 to 2 (a2)+1-b2

B2+c2 is equal to, or greater than 1

The instantiation that can be used for ruthenium Base Metal cyclopentadinyl compound of the present invention sees Table 1 and Fig. 5.

Table 1

The 1-methyl, 1 '-the ethyl ruthenocene	1,2-dimethyl, 1 '-the ethyl ruthenocene
		The 1-methyl, 1 '-the propyl group ruthenocene	The 1-methyl, 1 ', 3-diethyl ruthenocene
The 1-methyl, 1 '-the isopropyl ruthenocene	The 1-methyl, 1 ', 2-diethyl ruthenocene
		The 1-methyl, 1 '-the butyl ruthenocene	The 1-methyl, 1 '-ethyl, 3-propyl group ruthenocene
The 1-methyl, 1 '-the sec-butyl ruthenocene	The 1-methyl, 1 '-propyl group, 3-ethyl ruthenocene
		The 1-methyl, 1 '-tert-butyl group ruthenocene	The 1-ethyl, 1 '-methyl, 3-propyl group ruthenocene
The 1-ethyl, 1 '-the propyl group ruthenocene	The 1-methyl, 1 '-ethyl, 2-propyl group ruthenocene
		The 1-ethyl, 1 '-the isopropyl ruthenocene	The 1-methyl, 1 '-propyl group, 2-ethyl ruthenocene
The 1-ethyl, 1 '-the butyl ruthenocene	The 1-ethyl, 1 '-methyl, 2-propyl group ruthenocene
		The 1-ethyl, 1 '-the sec-butyl ruthenocene	The 1-methyl, 1 '-the propyl group ruthenocene
The 1-ethyl, 1 '-tert-butyl group ruthenocene	The 1-methyl, 1 '-the ethyl ruthenocene
		The 1-propyl group, 1 '-the isopropyl ruthenocene	1,3-dimethyl, 1 '-the ethyl ruthenocene
The 1-propyl group, 1 '-the butyl ruthenocene	1,2,1 '-dimethyl, 3 '-the ethyl ruthenocene
		The 1-propyl group, 1 '-the sec-butyl ruthenocene	The 1-butyl, 1 '-the acetyl group ruthenocene
The 1-propyl group, 1 '-tert-butyl group ruthenocene	The 1-ethyl, 1 '-the methoxyl group ruthenocene
		The 1-isopropyl, 1 '-the butyl ruthenocene	The 1-ethyl, 1 '-methoxyl group-2-ethyoxyl ruthenocene
The 1-isopropyl, 1 '-the sec-butyl ruthenocene	1,2,3,4-tetramethyl, 1 '-the ethyl ruthenocene
		The 1-isopropyl, 1 '-tert-butyl group ruthenocene	The 1-acetyl group, 1 '-the ethyoxyl ruthenocene
The 1-butyl, 1 '-the sec-butyl ruthenocene	The 1-difluoromethyl, 1 '-the ethyl ruthenocene
		The 1-butyl, 1 '-tert-butyl group ruthenocene	The 1-trifluoromethyl, 2,3,4-fluoro-1 '-the trifluoromethyl ruthenocene
1-sec-butyl ruthenocene, 1 '-tert-butyl group ruthenocene	The 1-vinyl, 1 '-the fluorine ruthenocene
		1,1 ', 3-trimethyl ruthenocene	The 1-ethoxyl methyl, 1 ', 2 '-the diethyl ruthenocene
1,1 ', 2-trimethyl ruthenocene	The 1-ethyl, 1 '-the propoxyl group ruthenocene
		1,3-dimethyl, 1 '-the ethyl ruthenocene	1,1 ', 2,4-triethyl group-3 '-the acetyl group ruthenocene

The spendable Metallocenic compound of the present invention also comprises similar table 1 or osmium base and Fe-base compound shown in Figure 5. Equally, the inventive method can be used for generation and comprises other ηⁿThe Metallocenic compound of-coordination aromatic portion.

In another U.S. Patent application of submitting to simultaneously with the application of David M.Thompson and Cynthia A.Hoover, announced the suitable metal cyclopentadinyl compound that can be used for the inventive method, this application name is called asymmetric 8 families (VIII) Metallocenic compound, attorney docket D-21266, this application is attached to herein by reference.

In another United States Patent (USP) of submitting to simultaneously with the application of David M.Thompson and Cynthia A.Hoover, announced the suitable synthetic method that preparation can be used for the Metallocenic compound of the inventive method, this application name is called the method for preparing Metallocenic compound, attorney docket D-21245, this application is attached to herein by reference.

Slaine can be metal (III) salt, for example metal halide (such as chloride, bromide, iodide, fluoride), metal nitrate and other suitable slaine. M is 8 families (VIII) metals, for example Ru, Os or Fe. Usually slaine is abbreviated as MX_n The MX that writes a Chinese character in simplified form used herein_nDo not repel the metal salt compound that contains in conjunction with water, contain in conjunction with the metal salt compound of water and can more clearly use formula MX as everyone knows in this area_n·μH ₂O represents that wherein μ is not 0. So in instantiation, the FeX that writes a Chinese character in simplified form used herein₃Comprise anhydrous and contain molysite in conjunction with water, these molysite can be for the preparation of ferrocene or ferrocene compounds.

Metal (M) salt (X) can be metal (III) salt, for example metal halide (such as chloride, bromide, iodide, fluoride), metal nitrate and other suitable slaine. Metal formula MX_nMore specifically expression if perhaps have in conjunction with water, is used formula MX_n·μH ₂O represents. M is Ru, Os or Fe. Slaine such as FeX₃·ηH ₂O or FeX₃For the preparation of ferrocene or ferrocene compounds.

Part (L) is generally the electron pair donor compound. Neutral electron pair donor such as triphenylphosphine (PPh₃) be applied in one embodiment. Also can use tricyclohexyl phosphine and other general formula PR₃Phosphine and tris phosphite P (OR)₃, wherein R is phenyl, cyclohexyl, alkyl or branched alkyl such as the tert-butyl group. Other suitable electron pair donor comprises amine, phosphate, carbonyls, alkene, polyolefin, chelating phosphine, chelating amine etc.

The Cp compound is the precursor of the Cp part of above-mentioned CpMCp ' compound. Preferred Cp compound is HCp, such as cyclopentadiene or indenes. The Cp component also can be cyclopentadienyl group or indenyl anion salt, such as cyclopentadiene potassium (KCp), and cyclopentadiene sodium (NaCp), cyclopentadiene lithium (LiCp) etc. The suitable cation that uses with cyclopentadienyl anion in the synthetic method described herein comprises trimethylsilyl (TMS), Na, Li, K, Mg, Ca and Tl.

At least one hydrogen atom of Cp part is by D as mentioned above₁Group displacement. The instantiation of HCp comprises methyl cyclopentadiene, ethyl cyclopentadiene, n-pro-pyl or isopropyl cyclopentadiene, normal-butyl, sec-butyl or tert-butyl group cyclopentadiene, perhaps halo cyclopentadiene etc.

The Cp compound also can be two replacements or polysubstituted, as is two, three, four and five substituted-cyclopentadienyls. Substituent group D₂、D ₃、D ₄And D₅Instantiation as mentioned above.

MX _n, L and HCp component all can respective pure form or optionally comprise suitable solvent version and provide. The used preferred solvent of method of the present invention comprises alcohol such as ethanol, methyl alcohol, isopropyl alcohol and other alcohol. Also can use ethyl acetate, oxolane (THF), saturated or unsaturated hydrocarbons, aromatic heterocycle, alkyl halide, silylanizing hydrocarbon, ether, polyethers, thioether, ester, lactone, acid amides, amine, polyamine, nitrile, silicone oil and other aprotic solvent. Also can use combination solvent.

Common MX_n, L and Cp concentration selection be well known in the art. MX for example_nMolar concentration in suitable solvent can be about 0.1M to respective pure form. The molar concentration of L in suitable solvent can be about 0.1M to respective pure form. The molar concentration of Cp in suitable solvent can be about 0.1 to respective pure form. If use the phosphine of respective pure form then react strong heat release. Method and the system of a large amount of reaction heat of dissipation per unit volume are well-known in this area.

Described three components can any sequential combination. In one embodiment, metal component and HCp component join in the L component simultaneously. In another embodiment, then metal component and HCp combination of components form mixture mixes mixture with the L component, for example realizes by the L component is added in the mixture. In another embodiment, all components mixes simultaneously.

HCp and MX_nMol ratio be generally about 50 to about 1, preferred about 12 to about 2 and most preferably from about 7 to about 5. L and MX_nMol ratio be generally about 8 to about 0, preferred about 6 to about 2 and most preferably from about 5 to about 3.5. If use quite excessive HCp component, reaction will generate (Cp)₂The M product.

Reaction temperature is preferably near the boiling point of employed solvent or the boiling point of reactant mixture. Other suitable temperature can be determined by normal experiment. Usually reaction can be carried out under near the temperature of boiling point being higher than the response composite freezing point. For example reaction can carried out between-100 ℃ to about 150 ℃ approximately.

Reaction time is usually depended on the concentration of temperature and each reactant and can be for example about 5 minutes to about 96 hours.

MX _n, the intermediate component that generates of the reaction of L and HCp can use formula CpML_fX represents, wherein f=1 or 2.

Separate by methods known in the art in one embodiment as be the CpML of solid_fX. Make subsequently midbody compound CpML_fX and the reaction of Cp ' compound (preferably reaction in the presence of solvent). Cp ' compound preferably contains the anion of the Cp part of the invention described above compound. Counter ion counterionsl gegenions comprise trimethylsilyl (TMS), Na, Li, K, Mg, Ca and Tl. The instantiation of operable cyclopentadienyl compounds is including but not limited to ethyl cyclopentadiene sodium or lithium, methyl cyclopentadiene sodium or lithium, isopropyl cyclopentadiene sodium or lithium etc. Also can use two of Cp part to replace or polysubstituted anion (such as two, three, four or five substituted cyclopentadienyl anion). Also can use the anion that does not replace as mentioned above indenes, cyclic polyolefin, poly-ring-type unsaturated hydrocarbons, heterocycle and aromatic ring.

In an instantiation, midbody compound is CpRu (PPh₃) ₂Cl. This compound and Cp ' reactant salt. Cp ' salt of recommending comprises NaCp ', LiCp ', (Cp ')₂Mg, TMS (Cp ') and (Cp ') Tl.

The example of suitable solvent comprises benzene,toluene,xylene, pentane, hexane, benzinum, fragrant heterocycle, saturated or unsaturated hydrocarbons, alkyl halide, silylanizing hydrocarbon, ether, polyethers, thioether, ester, lactone, acid amides, amine, polyamine, nitrile, polysiloxanes etc.

Usually the molar concentration of Cp ' component in solvent arrives about 3.5M for about 0.1M, and preferably about 0.5M arrives about 2.5M and most preferably from about 1.4 arrives about 1.8M.

Cp ' and CpML_fThe mol ratio of X is generally about 50 to about 1, preferred about 6 to about 1 and most preferably from about 1.6 to about 1.2.

Do not isolate in another example intermediate CpML_fThe X component. After forming midbody compound in the solution, Cp ' compound (as mentioned above salt form) adding is contained CpML_fIn the solution of X.

Cp ' component and intermediate CpML_fThe reaction of X (no matter whether separating) is carried out under temperature as mentioned above and is generated CpMCp ' product.

Reaction time is depended on temperature and each reactant concentration usually, can be about 15 minutes to about 6 days.

When synthetic CpRuCp ' type structure, and a ring comprises ketone, ester or ether function base in this structure, then preferably has the ring of greater number ketone, ester or ether as Cp ' ring, and it is joined intermediate as TMS salt.

Product CpMCp ' can separate and/or purifying by methods known in the art, for example then distillation of solvent (such as hexane) extraction, distillation or chromatography or directly by distillation, distillation or chromatography separation and/or purifying.

Also can use recrystallization, ultracentrifugation and other technology. Perhaps product can the reactant mixture form be further used and need not further be separated and/or purifying.

Chemical reaction shown in Figure 6 has been described a kind of method for preparing the compounds of this invention. In the described method of Fig. 6, MCl₃·μH ₂O, triphenylphosphine and D₁The cyclopentadiene back flow reaction in ethanol that replaces generates midbody compound CpM (PPh₃) ₂Cl, this midbody compound then with D₁The cyclopentadiene sodium reaction of ' replacement generates CpMCp '.

One of Cp and/or Cp ' or the two can comprise other substituent group D x, for example group as mentioned above. One of Cp and/or Cp ' or the two can be two, three, four or five substituted-cyclopentadienyl parts.

Figure 7 shows that can be used for generating specific two replaces asymmetric ruthenocene such as 1-methyl, 1 '-ethyl ruthenocene or (methyl cyclopentadienyl) (ethyl cyclopentadienyl group) close the synthetic schemes of ruthenium. As shown in Figure 7, RuCl₃·XH ₂O, triphenylphosphine and methyl cyclopentadiene back flow reaction in ethanol generates midbody compound chlorine (methyl cyclopentadienyl) two (triphenylphosphines) and closes ruthenium (II) or (η⁵-C ₅H ₄C ₂H ₅)Ru(PPh ₃) ₂Cl, then the reaction of this midbody compound and ethyl cyclopentadiene sodium generates the 1-methyl, 1 '-the ethyl ruthenocene.

Technical examples for the compound that characterizes above-mentioned synthetic method generation includes but not limited to analyze gas-chromatography, nuclear magnetic resonance (NMR), TGA (TGA), inductivity coupled plasma mass spectrometry (ICPMS), vapour pressure and viscosity measurement.

The relative vapour pressure of above-mentioned precursor or relative volatility can be measured by thermogravimetry technology well-known in the art. Equilibrium vapor pressure also can be by following mensuration: then all gas in the closed container of finding time import the compound steam in the described container and with method mensuration pressure well-known in the art.

Do not explain the present invention although stick to specific mechanism, think the various character of specific function change 8 families (VIII) metallocene of each Cp and Cp ' ring, such as solubility, vapour pressure, decomposability, combustibility and other reaction path, reducing/oxidizing electromotive force, geometric configuration, preferred orientation and electron density distribution etc. For example, think larger substituent group D₁And/or D₁' cause the increase of molecule entropy, this so that Metallocenic compound of the present invention and published Compound Phase than more being tending towards at room temperature being in a liquid state.

Above-mentioned Metallocenic compound occurs to decompose and eliminate organic moiety in the inventive method, generates 8 families (VIII) Metal Substrate or 8 families (VIII) metal oxide base film, coating or powder.

For being highly suitable for original position, the precursor of liquid prepares powder or coating under the room temperature described herein. For example a kind of Liquid precursor can be coated to substrate and then be heated to the temperature that enough makes described precursors decompose, thereby eliminate organic group and form metal or coating of metal oxides in substrate. Can be by whitewashing, spray, flood or other technology well-known in the art being coated to substrate with Liquid precursor. Can in baking oven, utilize fan heater to heat by electric heating heating substrate or by other method well-known in the art. Stacked coating can be by applying a kind of precursor and heating be decomposed to form the ground floor coating, then applies at least one other coating with identical or different precursors and heat and make.

The luxuriant precursor of liquid metals is also aerosolizable and spray in the substrate as mentioned above. Available atomizing and Spray painting tool such as nozzle, sprayer etc. are well-known in the art.

Metallocene or class of metallocenes compound are applied to gas phase deposition technology and form powder, film or coating as mentioned above in the preferred embodiment of the invention. Described compound can be used as single-source precursor and uses, and perhaps unites use with one or more other precursors, for example unites use with at least a other metallo-organic compound or the metal complex steam that adds thermosetting. Also can be applied in the given method more than a kind of as mentioned above metallocene precursors.

Can in the presence of other gaseous component, deposit. In one embodiment of the invention, in the presence of at least a non-reactive carrier gas, carry out the film deposition. The example of non-reactive carrier gas comprises inert gas, as nitrogen, argon gas, helium and as described under the process conditions not with other gas of precursors reaction. In other embodiments, in the presence of at least a active gases, carry out the film deposition. Some operable active gases is including but not limited to hydrazine, oxygen, hydrogen, air, oxygen-enriched air, ozone (O₃), nitrous oxide (N₂O), steam, organic vapor etc. As well known in the art, at a kind of oxidizing gas (for example air, oxygen, oxygen-enriched air, O₃、N ₂The steam of O or oxidisability organic compound) is conducive to generate metal oxide film under the existence. Think D₁、D ₁′、D _xAnd D_xThe existence of oxygen atom also is conducive to generate metal oxide in the ' organic group.

Deposition process described herein can form film, powder or the coating that comprises single metal (for example osmium) or comprise single metal oxide (RuO for example₂) film, powder or coating. Also can deposit hybrid films, powder or coating, for example mixed metal oxide film. Can several metal organic precursors prepare mixed metal oxide film by for example utilizing, wherein at least a precursor is selected from above-mentioned metallocene or class of metallocenes compound.

Carry out gas phase membrane and deposit to generate the rete of desired thickness (for example about 1nm is to being thicker than 1mm). Precursor described herein is particularly useful for preparing film (for example thickness is the film of about 10nm to about 100nm). For example the ruthenium film can be considered for the manufacture of metal electrode, particularly the capacitance electrode of p channel logic metal electrode and DRAM device.

This method also is applicable to prepare stacked film, wherein at least two coating phases or form different. The stacked film example comprises metal-insulator semiconductor (MIS) and metal-insulator-metal type (MIM).

In one embodiment, the present invention relates to a kind of method, described method comprises by the mode of heat, chemistry, photochemistry or excitation of plasma decomposes aforesaid metallocene or class of metallocenes precursor (compound shown in for example a kind of table 1), thereby forms the step of film in substrate. For example, steam and substrate contact that described compound (being liquid under the preferred room temperature) generates, the temperature of substrate is enough to the decomposing metal cyclopentadinyl compound, and forms the film that one deck comprises 8 families (VIII) metal or 8 families (VIII) metal oxide in substrate.

Described precursor can be applied to chemical vapour deposition (CVD) (CVD) or more particularly, is applied to metal organic chemical vapor deposition well-known in the art (MOCVD) technique. For example above-mentioned precursor can be used for the CVD technique under atmospheric pressure and the low pressure. Described compound can be used for hot wall type CVD (a kind of method that heats whole reative cell) and cold wall or warm wall type CVD (technology of a kind of heating substrate).

Above-mentioned precursor also can be used for plasma or optics assisted CVD technique, wherein is used for exciting cvd precursor from the energy of plasma or electromagnetic-energy respectively. Described compound also can be used for ion beam, electron beam assisted CVD technique, and wherein ion beam or electron beam point to respectively substrate to provide the decomposition cvd precursor required energy. Also can use laser assisted CVD technique, wherein laser beam points to substrate to excite the photolysis of cvd precursor.

The inventive method can be carried out in various CVD reactors, the hot wall that for example is well known in the art or cold wall reactor, plasma is auxiliary, the particle beams auxiliary or the laser assisted reactor in carry out.

Be the precursor of liquid under the usually preferred room temperature during CVD makes, the character of above-mentioned several asymmetric ruthenocene compounds makes it be suitable for use as cvd precursor. 1-methyl for example, 1 '-fusing point of ethyl ruthenocene is 2 ℃. The 1-ethyl, 1 '-fusing point of isopropyl ruthenocene is 3 ℃; The 1-methyl, 1 '-be liquid under the isopropyl ruthenocene room temperature. Previous used symmetry 1,1 '-fusing point of diethyl ruthenocene is 6 ℃, and 1-ethyl ruthenocene fusing point is 12 ℃.

The examples of substrates that available method of the present invention applies comprises solid substrate, the substrate of making such as following material: metal (such as Al, Ni, Ti, Co, Pt, Ta); Metal silicide is (such as TiSi₂、 CoSi ₂、NiSi ₂); Semi-conducting material (such as Si, SiGe, GaAs, InP, diamond, GaN, SiC); Insulator is (such as SiO₂、Si ₃N ₄、HfO ₂、Ta ₂O ₅、Al ₂O ₃, barium strontium titanate (BST)); Barrier material (TiN, TaN); Perhaps comprise the combination of described material in substrate. In addition, film or coating can be at glass, pottery, and plastics generate on thermoset polymerization material and other coating or the rete. In preferred embodiments, the film deposition is to generate in the substrate that is used for electronic device manufacturing or processing. In other embodiments, use substrate to support the low resistivity conductor deposit, it is stable that described deposit keeps in the presence of oxidant and in the high temperature, for example Ru metal or RuO₂Film, perhaps light-transmissive film such as RuO₂。

The inventive method is used in deposited film in the substrate with smooth planar surface. In preferred embodiments, adopt described method deposited film in the substrate that is used for wafer manufacturing or processing. For example, adopt described method comprising raceway groove, deposited film on the band patterned substrates of the features such as hole or path. In addition the inventive method also can with other step (for example sheltering etching etc.) combination of wafer manufacturing or processing.

CVD or MOCVD film can be deposited into desired thickness. For example thickness can less than 1 micron, preferably less than 500 nanometers, be more preferably less than 200 nanometers. Also can make thickness less than 50 nanometers, for example thickness is about 20 films to about 30 nanometers.

Above-mentioned asymmetric Metallocenic compound also can be used for ald (ALD) or the atomic layer of utilizing of the present invention and become the nuclear technology film former, wherein substrate is exposed in the ALT pulse of precursor, oxidant and inert gas flow. The pantostrat deposition technique is seen and is set forth in such as the U.S. Patent number 6,287,965 that is issued to September 11 calendar year 2001 such as kang etc. and the U.S. Patent number 6,342,277 that was issued to Sherman on January 29th, 2002. Described two patents are attached to herein by reference.

For example in the ALD circulation, substrate is exposed to step by step: a) inert gas; B) inert gas carrying precursor vapor, c) inert gas; And d) oxidant (share separately or with inert gas). In general, each step can be the as far as possible short distance that equipment can allow (for example millimeter) and process requires as far as possible for a long time (for example several seconds or a few minutes). The cycle of a circulation may be as short as in millisecond meter also can grow to minute. Circulation can repeat a few minutes by several hours. The thickness of institute's produced film can be several nanometer thin or thicker, for example 1 millimeter (mm).

The inventive method also can be used supercritical fluid. The example of the film deposition method of current use supercritical fluid well-known in the art comprises chemical fluid deposition (CFD); Supercritical fluid transmission-chemical deposition (SFT-CD); Supercritical fluid chemical deposition (SFCD); And supercritical impregnation deposition (SFD).

For example the CFD method is applicable to well generate high purity films and covers complex surface and fill the high length-diameter ratio parts. CFD sees and is set forth in as being issued to the U.S. Patent number 5,789,027 of Watkins etc. on August 4th, 1998. Use the supercritical fluid film forming also to see to be set forth in as being issued to U.S. Patent number 6,541,278 B2 of Morita etc. on April 1st, 2003. Described two patents are attached to herein by reference.

In one embodiment of the invention, with the band patterned substrates of heating at solvent such as nearly critical or supercritical fluid (such as nearly critical or supercritical CO₂) exist down, be exposed in one or more precursors, precursor shown in one or more tables 1 (such as the 1-methyl, 1 '-the ethyl ruthenocene). If use CO₂, solvent fluid pressure is higher than about 1000psig (pound per square inch (gauge pressure)), and temperature is at least about 30 ℃.

Described precursor decomposes generation 8 families (VIII) metal film in substrate. Described reaction also generates organic matter from Cp and the Cp ' part of precursor. Described organic matter is dissolvable in water in the solvent fluid and removes from substrate easily. For example use oxidizing gas also can generate metal oxide film.

In one embodiment, deposition process is carried out in the reative cell of one or more substrate is housed. By heating whole reative cell (for example using heating furnace) substrate is heated to required temperature. Can generate the Metallocenic compound steam by the method that reative cell is vacuumized. For low-boiling compound, thermal reaction chamber can be added so that the compound gasification. When steam contacts the substrate surface of heat, produce metal or metal oxide film at described Surface disintegration. As mentioned above, metallocene or class of metallocenes precursor can use separately, also can unite use with one or more components (for example other metallorganic precursor, inert carrier gas or active gases).

Figure 8 shows that the sketch that uses method of the present invention to prepare an individual system of film. As shown in Figure 8, raw material is introduced the gas mix manifold containing with generative process gas, this gas is transported to deposition reactor for produced film. Raw material includes but not limited to carrier gas, active gases, purge gas, precursor, etching/purge gas etc. The accurate control that process gas forms can realize by mass flow controller well-known in the art (MFCs), valve, pressure sensor and miscellaneous equipment.

Fig. 8 also shows the by-pass of sending out the exhaust manifold of deposition reactor and being connected to vavuum pump for gas. The elimination system of vacuum pump downstream is used for removing any noxious material from Exhaust Gas.

Depositing system is equipped with situ analysis system, comprises the residual gas analyzer for the measuring process gas composition. Each procedure parameter of Control ﹠ data acquisition system monitoring (such as temperature, pressure, flow etc.).

Figure 9 shows that the sketch of device 10, described device is to can be used for preparing utilizing the inventive method to carry out the example of suitable device of the process gas of film deposition usefulness. Device 10 comprises gasifier 12, and liquid and solid precursor gasify by method well-known in the art herein. The temperature of precursor (determining its vapour pressure) is by the thermocouple monitoring and be heated by resistive device control. A suitable math equation that is used for relationship compound vapour pressure and temperature is:

lnP _sat＝A-B/T

1nP wherein_satBe the natural logrithm of saturated vapour pressure, A and B are that T is absolute temperature (opening) from experiment and theoretical constant.

Carrier gas (for example nitrogen) is transported to gasifier 12 from source of the gas 14 (for example gas tank). Required carrier gas flux is controlled by MFC16. The pressure of carrier gas is measured by pressure gauge 18. Valve 20 and 22 is used for the air-flow that control is transported to gasifier 12. Valve 24 and 26 is used for precursor vapor and the carrier gas air-flow of control output gasifier. Close bypass valve 28 with the carrier gas gasifier 12 that leads. The needle-valve 30 that is positioned at gasifier 12 downstreams is used for the stagnation pressure and the Process Gas air-flow that is transported to deposition reactor 32 of control gasifier.

The gas of supposing the output gasifier is fully saturated (for example dividing potential drop equals vapour pressure), and it is definite that the flow of precursor can utilize carrier gas flux, stagnation pressure and precursor vapor to press.

Figure 10 is the sketch of deposition reactor 32. The process gas that comprises carrier gas and vapor precursor imports through entrance 34. Also can come independent injection process gas, steam or supercritical fluid with a plurality of entrances or hole.

Thin film deposition is in substrate 36. Entrance 34 bottoms and substrate 36 tops keep fixed intervals. Substrate 36 is carried on the molybdenum pedestal 38 processed. Pedestal 38 is that a diameter is 3 to the maximum " the disk that can carry sample. Can revise reactor with deposited film in larger substrate, for example deposited film on 200 or 300 millimeters (mm) wafers.

Base-plate temp is measured with thermocouple 40, and controls with tungsten-halogen lamp 42. Deposition reactor pressure is monitored with capacitance manometer 44. In the film deposition process, substrate 36 is heated to temperature required, and contact with process gas. Use vavuum pump to reduce the interior pressure of deposition reactor.

In other embodiments, reative cell is equipped with field assay and/or automatic process control and data acquisition unit. Also can wait temperature control to process line and locular wall.

Usually the pressure in the deposition reactor 32 be about 0.01 holder to 760 holders, preferred about 0.1 holder to about 760 holders and most preferably from about 1 holder to about 50 holders.

The temperature of usually carrying out the film deposition is about 75 ℃ to about 700 ℃, preferred about 250 ℃ to 450 ℃.

As well known in the art, oxidizing gas such as air, oxygen, oxygen-enriched air, ozone (O₃), nitrous oxide (N₂O) or having of oxidisability organic compound steam be beneficial to the generation metal oxide film. Also can adopt well-known in the art other to be conducive to generate the technology of metal oxide film. The oxidant dividing potential drop is generally about 0 to about 50 holders. The mol ratio of oxidant and precursor is 0 to 10,000.

Above-mentioned precursor can be used for generating the film (for example osmium basement membrane) that comprises single metal, perhaps comprises single metal oxide (RuO for example₂) film. Also can deposit hybrid films, for example mixed metal oxide film. This class film is by for example utilizing several Organometallic precursors to generate, wherein at least a above-mentioned metallocene or the class of metallocenes compound of being selected from.

Can for example not generate metal film with carrier gas, steam or other source of oxygen yet.

The film that utilizes method described herein to generate can characterize with technology well-known in the art, for example utilize X-ray diffraction (XRD), auger spectrum, X-ray photoelectric emission spectrum (XPS), AFM (AFM), SEM and other technology well-known in the art. Also can utilize method well-known in the art to measure resistivity and the heat endurance of film.

Embodiment

Embodiment 1

Steps A

The middle pit of the stomach of 5L five neck round-bottomed flasks is equipped with the mechanical agitation oar. Then with ethanol (2.0L) and PPh₃(420g, 1.6mol) adds in this bottle. Two 500ml three-neck flask Teflon^Pipe (perfluorinated polymers, E.I.Du Pont Company) is connected to through displacement pump on two mouths of these 5L four neck flasks, remaining mouthful of this flask condenser pipe is installed. Heating jacket is placed in 5L flask bottom, and agitating solution also adds hot reflux. Triphenylphosphines all in backflow all are dissolved in the ethanol. When refluxing, nitrogen was passed into system about 30 minutes.

Meanwhile, with RuCl₃·XH ₂O (100g, 0.40mol), ethanol (300mL) and a Teflon^The magnetic stir bar that (perfluorinated polymers, E.I.Du Pont Company) coats is inserted in one of them 500ml round-bottomed flask. Ethanolic solution is brown/orange immediately. Need heated solution so that RuCl₃·XH ₂O all dissolves. Utilize slotting wearing in plug and importing solution of needle tubing that is connected to source nitrogen, use purging with nitrogen gas solution 30 minutes, and wear every filling in to discharge unnecessary pressure with another root needle tubing is slotting, the metering gauge pressure of described source nitrogen is 1-2 pounds/square inch (psig).

Preparation acetonitrile/the dry ice bath also immerses another 500ml flask wherein. The methyl cyclopentadiene (190g, 270mL, 2.4mol, fresh distillation under nitrogen protection) of fresh distillation is imported in the flask of described cooling with conduit.

After the ethanolic solution of triphenylphosphine and ruthenium trichloride was complete with purging with nitrogen gas, the content in two 500ml flasks pumped in the 5.0L flask by displacement pump with speed independently respectively, finished after being added on 5 minutes for two. For achieving this end, the ethyl cyclopentadiene is with the speed pumping of 45mL/min, and the ruthenium trichloride ethanolic solution is with the speed pumping of 50mL/min.

Add and solution was refluxed 2 hours after complete again. Can see that during this period tiny orange crystal is collected on the wall of solution meniscus top in the 2L flask.

Step B

Stir after 2 hours, with two displacement pumps on the 5L flask and Teflon^(perfluorinated polymers, E.I.Du Pont Company) pipe cuts off and connects. A distillation side arm is installed on the mouth of flask, removes about 1L ethanol by distillation. Stop mechanical agitation, make orange crystallization be deposited to drag. In 3 hours with the solution cool to room temperature. Insert the glass tube that an end is connected to the coarse sintering head in flask, decompression makes solution shift out flask through the sintering head. Crystal washs with heptane (300ml), and removes heptane with similar method. Carry out three washings.

Step C

All openings of flask are all used rubber stopper seal, the flask and re-fill nitrogen three times of finding time. THF (500ml, anhydrous) is imported flask and starts mechanical agitation. Then the THF solution (500mL, 1.2M, 0.60mol) with ethyl cyclopentadiene lithium imports in the 5L flask through conduit. These contents are added hot reflux and stirred 4 hours.

Reflux after 4 hours, stop to stir, solution is changed in the 2L one neck round-bottomed flask. On Rotary Evaporators, solution is concentrated to volume and is about 200ml. Then the liquid with this thickness changes in the 250ml round-bottomed flask.

Short-path distillation head and a 100ml storing received flask with the Wei Geluo depression is installed on the described 250ml round-bottomed flask. Distillating liquid under vacuum condition obtains the 1-methyl, 1 '-the ethyl ruthenocene, also contain simultaneously the clarification yellow liquid of some triphenylphosphines (measuring with GCMS). Yellow liquid is revolved the band distillation obtain 84.6g (productive rate 82%) purity greater than 99% (GCMS, 1H NMR) the 1-methyl without triphenylphosphine, 1 '-the ethyl ruthenocene, all the other impurity are 1,1 '-dimethyl ruthenocene and 1,1 '-the diethyl ruthenocene. TGA studies show that the Nonvolatile Residue of this liquid is less than 0.01%.

Embodiment 2

With a Teflon^(perfluorinated polymers, E.I.Du Pont Company) stirrer, ethanol (1.0L) and PPh₃(263g, 1.0mol, 5 equivalents) add in the 2L three neck round-bottomed flasks. With a 250ml dropping funel, a 150ml dipping bath chuck dropping funel and a condenser pipe are installed on three mouths of described 2L flask. Notice that two dropping funels are equipped with Teflon^(perfluorinated polymers, E.I.Du Pont Company) valve is so that environment facies isolation in they and the round-bottomed flask. A rubber is equipped with every plug in 150ml dipping bath chuck dropping funel top. Condenser overhead is equipped with a T joint and links to each other with inert gas. Place a heating jacket in 2L three neck round-bottomed flask bottoms, agitating solution also adds hot reflux. Triphenylphosphine all is dissolved in the ethanol in the backflow. System is used purging with nitrogen gas 3 hours during backflow.

Meanwhile, with RuCl₃·XH ₂O (50g, 0.20mol), ethanol (150mL, l equivalent) and a Teflon^The magnetic stir bar that (perfluorinated polymers, E.I.Du Pont Company) coats is inserted in the 500ml conical flask. Ethanolic solution is brown/orange immediately. Need mild heat solution so that RuCl₃·XH ₂O all dissolves. With described solution impouring 250ml dropping funel, a rubber is equipped with every plug in described dropping funel top. Utilize slotting wearing in plug and importing solution of needle tubing that is connected to source nitrogen, use purging with nitrogen gas solution 30 minutes, and wear every filling in to discharge unnecessary pressure with another root needle tubing is slotting, the metering gauge pressure of described source nitrogen is 1-2 pounds/square inch.

In 150ml dipping bath chuck dropping funel, prepare methyl alcohol/the dry ice bath. The inner chamber of described dropping funel adopts the method for similar other dropping funel of purge to use purging with nitrogen gas 30 minutes. Then methyl cyclopentadiene (6 equivalents distill in nitrogen twice for 96.2g, 1.2mol) is imported in the dropping funel of cooling every plug by rubber.

2L round-bottomed flask purge after 3 hours, will be completely cut off the Teflon of dropping funel and system remainder^(perfluorinated polymers, E.I.Du Pont Company) valve is all opened, and beginning drips two kinds of solution simultaneously. Described two kinds of solution all are added dropwise to PPh after 20 minutes₃In the ethanolic solution. Solution is in reflux state during this period. It is deeply tenne that solution is rapidly. After dropwising, solution was refluxed 2 hours again. Can see CpRu (PPh during this period₃) ₂The tiny orange crystal of Cl is collected on the wall of solution meniscus top in the 2L flask.

The pipeline that one end is connected with rough porous sintering head links to each other with displacement pump. The sintering end of pipeline is immersed in the reactor, pump all liq in the 2L round-bottomed flask. In this stage dropping funel is removed from reactor. At a mouth K head distillation joint is installed, the upper rubber of installing of another mouthful is every plug. Flask is found time and re-fill nitrogen three times. Under nitrogen protection, dry toluene (1.0L) is imported in the 5L flask every plug by rubber. This dark opaque solution is heated to backflow, opens K head distillation joint to evaporate a part of solvent. Collect distillate until tip temperature reaches 109 ℃ (noticing that in different experiments this will consume the solvent of different volumes-be generally 400-600ml liquid). Then solution is cooled to below the reflux temperature.

Extra toluene is added in the flask to obtain the toluene of the about 600ml of volume. Then the toluene slurry (35g, 0.35mol, 400mL) with ethyl cyclopentadiene lithium imports in the retort. Finish, under 80 ℃, solution was stirred 4 hours. In this stage flask is shifted out glove box, and remove most of toluene with K head distillation joint.

In remaining liquid (about 400ml) impouring 1.0L round-bottomed flask. Install one with the short-path distillation head of Wei Geluo depression and distillation at described round-bottomed flask. The liquid of collecting from the Wei Geluo rectifying column obtains the 1-methyl of the yellow liquid shape of 44g clarification with revolving the again distillation under vacuum condition of the band way of distillation, 1 '-the ethyl ruthenocene, purity is greater than 99% (GCMS). TGA studies show that the contained Nonvolatile Residue of this liquid is less than 0.01%.

Embodiment 3

Prepare as follows ethyl cyclopentadiene lithium. With Teflon^(perfluorinated polymers, E.I.Du Pont Company) stirrer is put into 2L three neck chuck round-bottomed flasks. With a stopcock joint, thermometer wrap pipe joint and the rubber with thermometer boss is installed on three mouths of described flask every plug. A nitrogen/vacuum manifold is connected on the stopcock joint, flask is found time to be filled with nitrogen three times again. Then dry toluene (1.0L) is imported in the flask and starts every plug by rubber and stir. A cryogenic liquid circulator is connected to the outer of chuck flask with the nalgene pipe puts, in the outer wall circulation cryogen (15 ℃) of chuck flask. In case toluene reaches-10 ℃, in ethyl cyclopentadiene (127g, 1.35mol) the importing flask with fresh distillation (in the midbarrel that a Wei Geluo rectifying column distills). (1.28mol), boot speed is lower than 0 ℃ with holding temperature and is as the criterion (importing about 2 hours) for 800 mL, 1.6M hexane solution slowly to import n-BuLi in the middle of stirring. In the process that imports n-BuLi, in the solution tiny white precipitate (ethyl cyclopentadiene lithium) can appear.

This product can suspension uses or is solid by filtering and removing separated from solvent.

Embodiment 4

THF (50mL, anhydrous, unrestraint agent), chlorine (ethyl cyclopentadienyl group) two (triphenylphosphines) are closed ruthenium (II) (3.22g, 0.004mol, l equivalent) and Teflon^(perfluorinated polymers, E.I.Du Pont Company) stirrer adds the 250ml flask that places nitrogen glove box. Agitating solution slowly adds the THF solution (0.20M, 30mL, 1.5 equivalents) of light violet magenta isopropyl cyclopentadiene sodium. Finish, solution is peony. Meniscus is yellow in 30 minutes. The solution stirring is spent the night.

Extracting sample aliquot (1.0ml) from solution analyzes with GC/MS. The peak that to observe a quality be 301g/mol and 1-ethyl-1 '-isopropyl ruthenocene consistent. Also observe other and alkyl cyclopentadiene dimer, 1,1 '-diethyl ruthenocene, 1,1 '-peak of the uniform quality of diisopropyl ruthenocene and triphenylphosphine.

Then under reduced pressure from flask, remove the THF solvent. At the 250ml flask vacuum jacket short-path distillation joint is installed, (～0.1 holder) distillation that the content in the flask is reduced pressure. Collect light yellow liquid (0.72g). Then with this liquid of chromatography purification. Use the pentane solution of silica gel. Post directly is 0.75 ", column length is 6 ". Utilize the look popularize law separate 0.53g purity for the 1-ethyl-1 of 99+% '-isopropyl ruthenocene (productive rate 41%).

Embodiment 5

With THF (50mL, anhydrous, unrestraint agent), chlorine (methyl cyclopentadienyl) two (triphenylphosphines) closes ruthenium (II) (5.02g, 0.007mol, l equivalent) and Teflon^(perfluorinated polymers, E.I.Du Pont Company) stirrer adds the 250ml flask that places nitrogen glove box. Agitating solution slowly adds the THF solution (0.20M, 50mL, 1.5 equivalents) of light violet magenta isopropyl cyclopentadiene sodium. Finish, solution is peony. Meniscus is yellow in 30 minutes. The solution stirring is spent the night.

Extracting sample aliquot (1.0ml) from solution analyzes with GC/MS. The peak that to observe a quality be 287g/mol and 1-methyl isophthalic acid '-isopropyl ruthenocene consistent. Also observe other and alkyl cyclopentadiene dimer, 1,1 '-dimethyl ruthenocene, 1,1 '-peak of the uniform quality of diisopropyl ruthenocene and triphenylphosphine.

Then under reduced pressure from flask, remove the THF solvent. At the 250ml flask vacuum jacket short-path distillation joint is installed, (～0.1 holder) distillation that the content in the flask is reduced pressure. Collect light yellow liquid (1.78g). Then with this liquid of chromatography purification. Use the pentane solution of silica gel. Post directly is 0.75 ", column length is 6 ". Utilize the look popularize law separate 1.03g purity for the 1-methyl isophthalic acid of 98+% '-isopropyl ruthenocene (productive rate 53%).

Embodiment 6

Two (propyl group cyclopentadienyl group) closed magnesium (5.15g, 0.02mol, 1 equivalent), and chlorine (methyl cyclopentadienyl) two (triphenylphosphines) closes ruthenium (II) (5.02g, 0.007mol, 1 equivalent) and Teflon^(perfluorinated polymers, E.I.Du Pont Company) stirrer adds the 250ml flask that places nitrogen glove box. Toluene (120ml, anhydrous, unrestraint agent) is imported the 250ml round-bottomed flask, stir content. Solvent finishes, and solution is peony.

Then under reduced pressure from flask, remove toluene solvant. Decompression removes toluene solvant, and at flask short neck distillation joint is installed. Collect distillate, GC/MS show short neck distillation main fractions be the 1-propyl group-1 of 88.7% purity '-the ethyl ruthenocene.

Embodiment 7

Measure the vapour pressure of ruthenium precursor. Under temperature (25-70 ℃) (MeCp) (EtCp) vapour pressure of Ru be at least (EtCp)₂The twice of Ru.

Use is with the glove box of inert gas environment, will about 1g (MeCp) (EtCp) Ru put into gasifier. Substrate is at room temperature cleaned with ultrasonic wave before deposition.

Substrate is washed by 1 minute interval, at first uses H₂The O flushing is then with 1: 1: 5-NH₄OH∶H ₂O ₂∶H ₂O solution is used H at last₂The O flushing. Then use the nitrogen drying substrate. Import sample and shift out sample by using a load chuck (load-lock) that is equipped with the magnetic couple conveying arm to finish from reactor to reactor.

In case load substrate and be positioned the heater top, the film deposition will be carried out in the following order. At first substrate is heated to temperature required. Then sample is exposed in the process gas that contains precursor (or various precursor) and any co-reactant (for example oxidant). Use the nitrogen of ultra-high purity (UHP, purity is greater than 99.999%) as carrier gas and washing gas. UHP oxygen is as oxidizing gas. Close ruthenium with UHP nitrogen gasification precursor (methyl cyclopentadienyl) (ethyl cyclopentadienyl group).

Embodiment 8

Use Fig. 9 and 10 shown devices at silica (SiO₂Deposit ruthenium film in)/silicon (Si) substrate. Table 2 has briefly been explained reaction condition and result. In all these experiments, total gas flow rate is fixed on 750 standard cubic centimeters per minute (sccm), and precursor flow rate is 0.4sccm. Base reservoir temperature is measured with the dual wavelength pyrometer that the Williamson Co. that is positioned at Massachusetts state Concord produces. Reactor pressure uses the hot Baratron electric capacity barometer of being produced by the MKS Instruments company that is positioned at Massachusetts state Andover to measure, and described barometer range is 0.1 to 1000 holder. The gap refers to the distance between process gas inlet tube and the coated substrate, and unit is inch. The flow of oxygen is adjusted according to ratio in the table 2. Balance Air is nitrogen. O₂With the ratio of precursor be that the oxygen molar flow is divided by the molar flow of precursor in the process gas. As shown in table 2, substrate is exposed to whole process gas mixture (steam, O₂Reactant gas, N₂Carrier gas) time is 15 to 60 minutes.

Table 2

Experiment	Sedimentation time, minute	T， ℃	P, holder	The gap, inch	O 2/ precursor ratio	Purpose	Remarks
								(a)	30	240	30	1	50	Deposited film	Attempt first, without visible deposition
(b)	60	360	2	1	500	Deposited film	Successfully deposit first
								(c)	15	360	2	2	500	Improve uniformity by strengthening the gap	Pyrometer output is waved, and shows the film growth
(d)	15	360	2	2	50	By reducing O2Improve uniformity to about 50 with the precursor ratio	Uniformity is better than experiment (b)
								(e)	15	280	20	2	50	At lower temperature and growth ruthenium film under the high pressure more	Without visible deposition
(f)	15	360	2	2	50	Whether repeat (d) exhausts in experiment (e) to observe precursor	Similar to (d), slightly meagre (precursor approaches or exhausts fully)

The thickness of deposited film is measured with cross section SEM (SEM). Sheet resistance and corresponding resistivity are measured with 4 point probes. Element forms available various technology to be determined, comprises energy-dispersive spectroscopy (EDS) and XPS. Figure 11 and 12 shows that experiment (d) sample that obtains with SEM is in the cross sectional view at 75 degree inclination angles. The film for preparing under experiment (d) condition has good thickness evenness and resistivity. The ruthenium film thickness is about 200 nanometers (nm). Sheet resistance is measured as 0.11 Ω/sq with 4 point probe method. Consequently resistivity is 22 μ Ω cm. Energy-dispersive spectroscopy shown in Figure 13 (EDS) spectrogram has been proved conclusively SiO₂There is thin layer ruthenium film in the/Si substrate.

Can expect and also can utilize the film for preparing thinner (for example thickness 20 to 30nm) such as the method that reduces sedimentation time.

Embodiment 9

Table 3 is depicted as experiment a-f (see and be set forth in embodiment 8) and other experiment 1-32. Employing is tested such as device as described in Fig. 9 and 10. As shown in table 3, substrate comprises SiO₂/ Si, aluminium oxide and band patterned wafers. All film sedimentation experiments all adopt the nitrogen of 100 standard cubic centimeters per minute (sccm) to be undertaken by precursor vaporizer. Gap among experiment c-f and the experiment 1-32 is 2 inches. (gap among the experiment a-b is one inch). Gasifier pressure is 250 holders in the experiment 15 and 18, is 50 holders in other experiment.

Table 3

Experiment	Precursor	Sedimentation time, minute	Base reservoir temperature ℃	The reactor pressure holder	Oxygen flow, sccm	Gasifier temperature ℃	Purpose	Remarks
									a	(MeCp)(EtCp)Ru	30	240	30	20	70	Growth Ru film	Employing (EtCp) (MeCp) Ru is attempted first
b	(MeCp)(EtCp)Ru	60	360	2	200	70	Growth Ru film	First successfully growth
									c	(MeCp)(EtCp)Ru	15	360	2	200	70	Improve uniformity by strengthening the gap	Pyrometer waves and shows the film growth
d	(MeCp)(EtCp)Ru	15	360	2	20	70	By reducing O2Improve uniformity to about 50 with the precursor ratio
									e	(MeCp)(EtCp)Ru	15	280	20	20	70	At lower temperature and growth ruthenium film under the high pressure more	Without visible growth
f	(MeCp)(EtCp)Ru	15	360	2	20	70	Whether repeat (d) exhausts in experiment (e) to observe precursor	Similar to 20021028B, slightly meagre (precursor approaches or exhausts fully)
									1	(MeCp)(EtCp)Ru	15	360	2	20	70	Increase pressure	Look than the faster growth of 2 holder experiments
2	(MeCp)(EtCp)Ru	15	350	2	20	70	Repeat (d) and (f) with the carrier pipe of new precursor and replacing	Without visible growth
									3	(EtCp) 2Ru	15	275	2	20	70	With (EtCp)2The Ru precursor repeats (1)
4	(EtCp) 2Ru	15	350	2	10	70	With 350 ℃ of repetitions of base reservoir temperature (2)
									5	(MeCp)(EtCp)Ru	15	350	2	10	70	O 2The flow repetition (1) that reduces by half is noted: pyrometer is proofreaied and correct again
6	(EtCp) 2Ru	5	350	2	10	70	Adopt (EtCp)2Ru is with (4) identical parameters
									7	(MeCp)(EtCp)Ru	30	350	2	10	70	Repeat (4) 5 minutes running times
8	(MeCp)(EtCp)Ru	5	350	20	10	70	In minimum temperature definite flow set is set, pedestal is initially set to 400C, operation deposition 30 minutes

Table 3, continuous

Experiment	Precursor	Sedimentation time, minute	Base reservoir temperature ℃	The reactor pressure holder	Oxygen flow, sccm	Gasifier temperature ℃	Purpose	Remarks
									9	(MeCp)(EtCp)Ru	5	350	20	10	70	Pressure is on the impact of nucleation density and growth rate
10	(MeCp)(EtCp)Ru	5/5	350	2	0/10	70	Front 5 minutes non-activity gas (O2) move then to observe whether improve nucleation density in 5 minutes with the active gases operation	Without obvious benefit
									11	(MeCp)(EtCp)Ru	180	348	2	10	70	Attempt first operation ALD program (details are referring to chart and notebook)	The situation that similar other Ru film occurs
12	(MeCp)(EtCp)Ru	12	303	20	10	70	The impact that under the constant pressures of 20 holders and lower base reservoir temperature, moves
									13	(MeCp)(EtCp)Ru	5.17	332	2	200	70	Utilize the parameter of (c) to determine RuO2Nucleation density
14	(MeCp)(EtCp)Ru	5	361	2	10	70	Process substrate with the Dave Thompson anthraquinone identical with (6)	Very coarse
									15	(MeCp)(EtCp)Ru	5	350	200	40	70	At constant pressure than high 2 orders of magnitude of previous experiment (2 holder to 200 holder) simultaneously with O2Ratio is brought up to and is tested (13) the consistent Ru of carrying out deposition	The film undergrowth
16	(MeCp)(EtCp)Ru	5	334	20	200	70	Constant pressure is that 20 holders repeat (13)
									17	(MeCp)(EtCp)Ru	5	353	2	10	70	Carry out the Ru deposition at " ideal " temperature conditions and lower carrier gas flux under the condition with reduction nozzle speed. Constant pressure keeps 2 holders (benchmark (6)).
18	(MeCp)(EtCp)Ru	2	354	20	10	70	With higher constant pressure and short as far as possible time cycle repetition (17)	Gasifier fault (250 holder)

Table 3, continuous

Experiment	Precursor	Sedimentation time, minute	Base reservoir temperature ℃	The reactor pressure holder	Oxygen flow, sccm	Gasifier temperature ℃	Purpose	Remarks
									19	(MeCp)(EtCp)Ru	2	355	20	10	70	Repeat (17) with the constant pressure of 20 holders and 2 minutes sedimentation time
20	(MeCp)(EtCp)Ru	3	302	20	200	70	High O2The thin film deposition of flow ruthenium-oxide thin layer
									21	(MeCp))(EtCp)Ru	5	304	2	200	70	Constant pressure is that 2 holders repeat (20)
22	(MeCp)(EtCp)Ru	5	330	2	200	70	Repeat (13)	Deposition is good
									23	(EtCp) 2Ru	5	331	2	200	70	With (EtCp)2The Ru precursor repeats (22)	Deposition is good
24	(MeCp)(EtCp)Ru	2	330	2	200	70	At band patterned wafers and other substrate (Al2O 3And SiO2) upper deposition Ru film
									25	(MeCp)(EtCp)Ru	10	329	2	200	70	Deposition of thick Ru film on the band patterned wafers	Deposition is good
26	(MeCp)(EtCp)Ru	120	345	2.3	10	70	Carry out the ALDRu deposition in band patterned wafers and other substrate
									27	(EtCp) 2Ru	5	333	2.4	200	90	By improving the gasifier temperature reduces (23) to 90 C sheet resistance with observation (22)	Deposition is good, the wafer middle section thicker/more coarse
28	(EtCp) 2Ru	5	333	2.5	200	80	Repeat under the gasifier temperature 80C (27)	Similar with 20030311A, slightly meagre
									29	(MeCp)(EtCp)Ru	5	332	2.2	200	90	Under 90C, use (MeCpEtCp) Ru precursor to repeat (27)	The thick film growth
30	(MeCp)(EtCp)Ru	5	331	2.2	200	80	Under 80C, use (MeCpEtCp) Ru precursor to repeat (29)	Similar with 20030312A, slightly meagre
									31	(MeCp)(EtCp)Ru	10	310	2.3	200	90	Maximum sedimentation rate under the lower base reservoir temperature	Not significant change
32	(MeCp)(EtCp)Ru	10	290	2.4	200	90	Continue lower base reservoir temperature	It is very good to deposit, and periphery is thicker

Following the carrying out of ALD test of experiment 11. Patterned wafer substrates is exposed in the process gas stream, and described process gas stream comprises the washing of (1) nitrogen; (2) nitrogen and precursor; (3) nitrogen washing; And (4) nitrogen and oxygen. The total cycle time (all 4 steps) of experiment 11 is 10 seconds (step 1 and 3 is 3 seconds, and step 2 and 4 is 2 seconds). Process circulation (all 4 steps) repeated 1080 times in 180 minutes. The thickness of gained film is about 65nm.

ALD carries out in a similar fashion in experiment 26, and total sedimentation time is 120 minutes. Deposition materials is not coalescent, but is that 50 to 300nm discrete nanocrystal forms by diameter.

Embodiment 10

Measure to use the 1-methyl, 1 '-character of the film of ethyl ruthenocene deposition and with 1,1 '-character of diethyl ruthenocene produced film compares.

Use and install as mentioned above deposited film on 3 inches wafers. Chip temperature is 330 ℃, and the precursor vaporized temperature is 70-90 ℃, and constant pressure is 2 holders, and oxygen flow is 200sccm, and nitrogen flow is 550sccm, and sedimentation time is 5 minutes, and layer-growth rate is 10-60nm/ minute.

Sheet resistance is measured with 4 point probes, and the vertical also interval 5mm with principal plane of described probe (principal plane=0mm).

The results are shown in Figure 14,15 and 16.

Figure 14 describes the film sheet resistance of measurement and the functional relation of gasifier temperature, and described film is with (EtCp)₂Ru and (EtCp) (MeCp) Ru deposit generation. Change the temperature of gasifier, and make all other experimental conditions (temperature, pressure etc.) keep fixing. Measure data at the substrate center. This figure shows (MeCp) the sheet resistance ratio use (EtCp) of the film of Ru deposition of use (EtCp)₂The sheet resistance of the film of Ru deposition is low. This can be owing under identical gasifier temperature, in the process gas (EtCp) (MeCp) concentration of Ru be higher than (EtCp)₂The concentration of Ru. Think that the difference of this precursor concentration derives from the difference of vapour pressure.

Cut wafer, see Figure 15 with the thickness that section S EM measures. Under cycle, use the 1-methyl at the same terms and same time, 1 '-thickness of the film of ethyl ruthenocene deposition greater than with 1,1 '-thickness of diethyl ruthenocene produced film. This result is also owing to the 1-methyl, 1 '-vapour pressure that the ethyl ruthenocene is higher.

The resistivity of these films shown in Figure 16 uses the measured value of sheet resistance and thickness to calculate.

The X-ray diffraction data show that also the viewed crystallite of SEM data is comprised of Ru. In addition, X-ray photoelectric spectroscopic data also is functional relation with the degree of depth of film. Described data show that there is oxygen in the film near surface and along with the degree of depth that enters film increases, the oxygen amount in the film reduces. Data show uses the 1-methyl, 1 '-oxygen in the film that the ethyl ruthenocene generates is less than with 1,1 '-the interior oxygen of film that the diethyl ruthenocene generates.

Be equal to statement

Although the present invention at length shows and be described with reference to its preferred embodiment, those skilled in the art can understand within not departing from the scope of the present invention that claims forgive, can make on the various forms and details on change.

Claims (10)

1. method for the preparation of film, described method is included in substrate and has at least a precursor of lower decomposition, and forms thus the step of film in described substrate, wherein realizes described decomposition by heat, chemistry, photochemistry or plasma exciatiaon, the general formula of described precursor is CpMCp '

Wherein

M is the metal that is selected from Ru, Os and Fe;

Cp is cyclopentadienyl group or the indenyl part of first replacement, and this part comprises at least one substituent group D₁；

Cp ' is cyclopentadienyl group or the indenyl part of second replacement, and this part comprises at least one substituent group D₁′；

Wherein

D ₁With D₁' difference;

D ₁Be selected from:

X；

C _a1H _b1X _c1；

C _a2H _b2X _c2(C＝O)C _a1H _b1X _c1；

C _a2H _b2X _c2OC _a1H _b1X _c1；

C _a2H _b2X _c2(C＝O)OC _a1H _b1X _c1 And

C _a2H _b2X _c2O(C＝O)C _a1H _b1X _c1；

Wherein

X is halogen atom;

A1 is 2 to 8 integer;

B1 is the integer of 0 to 2 (a1)+1-c1;

C1 is the integer of 0 to 2 (a1)+1-b1;

B1+c1 is at least 1;

A2 is 0 to 8 integer;

B2 is the integer of 0 to 2 (a2)+1-c2;

C2 is the integer of 0 to 2 (a2)+1-b2;

And

D ₁' be selected from:

X；

C _a1H _b1X _c1；

C _a2H _b2X _c2(C＝O)C _a1H _b1X _c1；

C _a2H _b2X _c2OC _a1H _b1X _c1；

C _a2H _b2X _c2(C＝O)OC _a1H _b1X _c1 And

C _a2H _b2X _c2O(C＝O)C _a1H _b1X _c1；

Wherein

X is F, Cl, Br or I;

A1 is 1 to 8 integer;

B1 is the integer of 0 to 2 (a1)+1-c1;

C1 is the integer of 0 to 2 (a1)+1-b1;

B1+c1 is equal to, or greater than 1;

A2 is 0 to 8 integer;

B2 is the integer of 0 to 2 (a2)+1-c2;

C2 is the integer of 0 to 2 (a2)+1-b2; And

B2+c2 is equal to, or greater than 1.

2. the process of claim 1 wherein that one of described Cp and Cp ' part or both comprise at least one other substituent group D_x, described D_xBe selected from:

X；

C _a1H _b1X _c1；

C _a2H _b2X _c2(C＝O)C _a1H _b1X _c1；

C _a2H _b2X _c2OC _a1H _b1X _c1；

C _a2H _b2X _c2(C＝O)OC _a1H _b1X _c1 And

C _a2H _b2X _c2O(C＝O)C _a1H _b1X _c1；

Wherein

X is F, Cl, Br or I;

A1 is 0 to 8 integer;

B1 is the integer of 0 to 2 (a1)+1-c1;

C1 is the integer of 0 to 2 (a1)+1-b1;

B1+c1 is equal to, or greater than 1;

A2 is 0 to 8 integer;

B2 is the integer of 0 to 2 (a2)+1-c2;

C2 is the integer of 0 to 2 (a2)+1-b2; And

B2+c2 is equal to, or greater than 1.

3. the process of claim 1 wherein that described precursor is vaporized and steam is imported into an inside and is equipped with in the deposition reactor of substrate.

4. the process of claim 1 wherein that described substrate is patterned wafer.

5. the process of claim 1 wherein that the steam of described precursor is combined with carrier gas.

6. the process of claim 1 wherein that the steam of described precursor is combined with the oxidisability component that is selected from oxygen, ozone and nitrous oxide.

7. the process of claim 1 wherein that described precursor is the 1-methyl, 1 '-the ethyl ruthenocene.

8. the process of claim 1 wherein that described film comprises at least a material that is selected from ruthenium metal, osmium metal, ferrous metal, ruthenium-oxide, somuum oxide and iron oxide.

9. the process of claim 1 wherein that described decomposition carries out in the presence of a kind of solvent fluid for nearly critical or supercritical fluid.

10. the process of claim 1 wherein that described film generates in substrate by the method for order chemical vapour deposition (CVD), atomic layer nucleation or ald.

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