Patent Application
20080081106
Generally, embodiments of the novel silicon precursor comprise a compound having the formula:
In one embodiment, Y comprises any hydrocarbyl group, for example, substituted or unsubstituted hydrocarbyl groups. The term “hydrocarbyl” as defined herein refers to any functional group comprising exclusively of carbon and hydrogen atoms. Example include without limitation, alkyl groups, alkenyl groups, alkynyl groups, aryl groups, or combinations thereof. Specific examples of alkyl groups include without limitation methyl, ethyl, propyl, butyl, etc. In addition, the hydrocarbyl groups may be branched or substituted hydrocarbyl groups such as secondary or tertiary alkyls. As used herein, “substituted hydrocarbyl” means a branched or substituted functional group containing exclusively hydrogen and carbon atoms. The hydrocarbyl groups preferably comprise 1 to 6 carbon atoms. However, Y may comprise hydrocarbyl groups with any number of carbon atoms.
In a particular embodiment, the silicon precursor comprises a disilazane. That is, Y comprises a nitrogen containing group having the formula N-Z where Z comprises a hydrogen group or a hydrocarbyl group. Example of suitable hydrocarbyl groups include alkyl groups such as without limitation, —CH3, —CH2CH3, —CH(CH3)2 or —C(CH3)3. However, Z may comprise any suitable hydrocarbyl group. In embodiments, Z comprises hydrocarbyl groups having from 1 to 7 carbon atoms. Nevertheless, Z may comprise hydrocarbyl groups with any number of carbons. In other embodiments, the silicon precursor comprises a disiloxane where Y is an oxygen atom.
R1, R2, R3, and R4, are, in general, hydrocarbyl groups or hydrogen groups. Examples of suitable hydrocarbyl groups include without limitation, alkyl groups, alkenyl groups, alkynyl groups, aryl groups, or combinations thereof. R1, R2, R3, and R4, typically comprise hydrocarbyl groups having 1 to 7 carbon atoms. However, R1, R2, R3, and R4, may comprise any suitable functional group such as a heterohydrocarbyl group. As defined herein, a “heterohydrocarbyl” is a hydrocarbyl group additionally containing nitrogen or oxygen. The heterohydrocarbyl group may or may not be substituted or branched. Examples of suitable heterohydrocarbyl groups include without limitation, —OCH3 and —N(CH3)2. R1, R2, R3, and R4, may each comprise the same functional group or different functional groups. In a preferred embodiment, R1 comprises the same functional group as R3 and R2 comprises the same functional group as R4.
In other embodiments, R1, R2, R3, and R4, each may comprise a cyclic functional group such as without limitation, a heterocyclic group, a cycloalkyl group having from 3 to 6 carbon atoms (i.e. a C3-C6 cyclic group), a benzyl group, or combinations thereof In one embodiment, R1, R2, R3, and R4, each form a heterocyclic ring with N as shown in the following structure:
The heterocyclic ring may comprise from 2 to 6 carbon atoms. In addition, other functional groups may be attached to the heterocyclic ring.
In some embodiments, X1, X2, X3, and X4 may each comprise hydrocarbyl groups, respectively, such as an alkyl group, an alkenyl group, an alkynyl group, an aryl group, or combinations thereof In other embodiments, X1, X2, X3, and X4 may each comprise hydrogen, respectively. Additionally, X1, X2, X3, and X4 may each comprise a heterohydrocarbyl group such as without limitation, an alkylamino or a dialkylamino group. However, it is contemplated that X1, X2, X3, and X4 may comprise any suitable functional group.
In a preferred embodiment, X1, X2, X3, and X4 may independently comprise hydrazino groups with the formula:
(R5)(R6)N—NH—
where R5 and R6 comprise the same functional groups as applied to R1, R2, R3, and R4, described above. R5 and R6 may comprise the same functional group or different functional groups. In an embodiment, R5 and R6 may bond with each other to form a cyclic functional group.
In some embodiments, X1, X2, X3, and X4 comprise the same hydrazino groups. For example, in an embodiment, the silicon precursor may comprise the following formula:
where R5 and R6 all comprise the same functional group. In a further embodiment, X1, X2, X3, and X4 comprise the same hydrazino group, as shown in the structure above, and R1, R2, R3, R4, R5 and R6 all comprise the same functional group. In other words, each Si atom in the —Si—Y—Si— group would be bonded to three identical hydrazino groups.
However, in other embodiments, X1, X2, X3, and X4 comprise different hydrazino groups. That is, even though X1 and X3 both comprise hydrazino groups, the R5 and R6 groups for each respective hydrazino group may comprise different functional groups, R5 and R6. Likewise, X1 and X2 may comprise different hydrazino groups and X3 and X4 may comprise different hydrazino groups.
In preferred embodiments, the silicon precursor is symmetric. In other words, the substituents for each Si atom are symmetrically distributed in relation with the —Si—Y—Si— group. Without limitation, examples of symmetric embodiments are shown below:
It is envisioned that the disclosed silicon precursors may comprise all isomers of the various embodiments described herein. In other embodiments, the silicon precursor is asymmetrical. In other words, the functional groups substituted on each Si atom in the —Si—Y—Si— bond may not be identical. In addition, the functional groups for each Si atom may be arranged differently. For illustrative purposes only, an embodiment of an asymmetrical silicon precursor is shown below:
Embodiments of the disclosed silicon precursor and its derivatives are characterized by a vaporization temperature of less than 500° C. Moreover, the disclosed compounds may deposit thin film at less than 550° C., preferably less than 500° C., more preferably less than 450° C. The silicon-containing films that are formed with embodiments of the silicon precursor may be used to form high k gate silicates, and silicon epitaxial films.
In a further embodiment, a method of depositing silicon film on a substrate comprises providing one or more of the disclosed silicon precursors. Providing the silicon precursor may entail introducing one or more of the disclosed silicon precursors into a reaction chamber. Other reactants may be introduced into the reaction chamber. For example, ammonia may be introduced along with the silicon precursor. Examples of other reactants that may be introduced include without limitation, hydrazine, amines, or combinations thereof. The reaction chamber may be of any configuration known to one of skill in the art. Examples of suitable reactors that may be used in conjunction with the disclosed precursors include without limitation, vertical tube reactors, horizontal tube reactors, hot wall reactors, cold wall reactors, barrel reactors, etc.
In an embodiment, the silicon precursor is diluted with an inert gas. Any suitable inert gas may be used such as Ar, He, N, or combinations thereof. Alternatively, one or more of the reactants are dissolved in a solvent to form a solution. According to one embodiment, the reactants or the solution may then be vaporized and reacted to form a vapor or a gas.
In an embodiment, a chemical reaction is initiated by the application of heat. Heat may be applied by any suitable means such as without limitation, thermal, convection, induction, conduction, plasma, etc. The reactants are vaporized at a temperature preferably at a temperature less than about 500° C., more preferably at a temperature less than about 450° C. The vapor is then allowed to diffuse on to a substrate. In general, the substrate is a wafer. Other examples of substrates include without limitation, SiC. The vapor contacts and adsorbs on to the substrate depositing the silicon film on the substrate. In other embodiments, the deposition of thin films using the disclosed precursors involves atomic layer deposition which is also well known in the art.
The aforementioned method is only one embodiment for which the disclosed silicon precursor may be utilized. In additional embodiments, the described silicon precursors may be used in processes such as plasma enhanced chemical vapor deposition, low pressure chemical vapor deposition, plasma-enhanced chemical vapor deposition, ultrahigh vacuum chemical vapor deposition, and atomic layer deposition. Other processes for which embodiments of the silicon precursor may be used include processes for depositing silicon-containing films such as silicon oxide, silicon oxynitride, or silicon nitride.
In another embodiment, a method of making a silicon precursor comprises the following reaction:
Cl3Si(H)CH2Si(H)Cl3+4 (CH3)2N—NH2+4 N(CH2CH3)3→[(CH3)2N—N(H)]2Si(H)CH2(H)Si[(H)N—N(CH3)2]2+4 N(CH2CH3)3.HCl
In an additional embodiment, a method of making a silicon precursor comprises the following reactions:
SiCl4+NH3→Cl3SiN(H)CiCl3
Cl3SiN(H)SiCl3+6(CH3)2N—NH2+6N(CH2CH3)3→[(CH3)2N—N(H)3]3SiN(H)Si[(H)N—N(CH3)2]3+6N(CH2CH3)3
While embodiments of this invention have been shown and described, modifications thereof can be made by one skilled in the art without departing from the spirit or teaching of this invention. The embodiments described herein are exemplary only and are not limiting. Many variations and modifications of the system and apparatus are possible and are within the scope of the invention. Accordingly, the scope of protection is not limited to the embodiments described herein, but is only limited by the claims which follow, the scope of which shall include all equivalents of the subject matter of the claims.
This application claims priority to U.S. provisional application Ser. No. 60/827,472, filed on Sep. 29, 2006 and incorporated herein by reference.
| Number | Date | Country | |
|---|---|---|---|
| 60827472 | Sep 2006 | US |
