Method of depositing thin group iiia metal films

This invention concerns a method of depositing thin metal films, particularly of aluminium.

The deposition of thin films of aluminium is important for a variety of applications, such as the metallisation of silicon devices in VLSI technology, the growth of semi-conducting III-V alloys eg. AlGaAs, AlInAs and AlSb and the growth of dielectrics, such as AlN. In addition, hybrid sensors based on digital recording media are currently under development which require the deposition of aluminium on micron-size steps or holes etched on silicon.

Metalorganic chemical vapour deposition (MOCVD) is an attractive thin film growth technique possessing the advantages of large area growth capability, accurate control of layer thickness and good conformal step coverage. Much effort has, therefore, been directed at developing suitable aluminium CVD precursors.

The use of metalorganic compounds of gallium as CBE precursors has been investigated (see Journal of Crystal Growth 120 (1992) 103-113 and 124 (1992) 81-87; Surface Science 278 (1992) 111-120) including the use of tritertiarybutylgallium, tri-isobutylgallium and tri-isopropylgallium. Whilst all the compounds gave rise to reduced carbon contamination of the metal film, tritertiarybutylgallium had unacceptably low growth rates.

Volatile metalorganic compounds of aluminium have been widely investigated as CVD precursors including trimethylaluminium, dimethylaluminium hydride and higher aluminium alkyls of the formula AlR₃ where R is n-propyl, n-butyl and i-butyl. However, aluminium film grown using these precursors have frequently demonstrated poor morphology and low purity. In particular, carbon contamination has resulted from the decomposition of the organic radical during metalorganic pyrolysis. That has stimulated research into the aluminium hydride based adducts bis-trimethylamine alane and dimethylethylamine alane from which carbon free aluminium and low carbon content AlGaAs have been grown. However, doubts remain about the large scale application of these alane adducts due to an unpredictable gas phase chemistry which can lead to premature decomposition and also their tendency to liberate hydrogen during storage at room temperatures.

The most successful and widely investigated CVD precursor to date has been triisobutylaluminium (TIBA). Detailed surface science studies have shown that at temperatures less than 327°C the facile β-hydride elimination of iso-butylene leads to carbon free aluminium films. However, at higher temperatures the iso butyl radical can eliminate a β -methyl group which leads to surface methyl radicals and to a significant increase in carbon content of the deposited aluminium film. That limits the temperature range for aluminium deposition from TIBA and precludes its use in the growth of technologically important Al/Si alloys, which require high substrate temperatures, typically above 400°C, to pyrolyze the silicon precursor, typically SiH₄.

Therefore, a need exists for an aluminium precursor which combines the advantages of stability associated with trialkylaluminium compounds with the potential to deposit high purity aluminium films.

It has now been surprisingly found that tritertiarybutyl aluminum may be used as a precursor for aluminium deposition.

Accordingly the present invention provides a method of depositing an aluminium film on a substrate comprising the steps of contacting the substrate with an aluminium precursor and treating the precursor to decompose leaving the aluminium deposited on the substrate, characterised in that the precursor is tritertiarybutyl aluminium.

The present invention further provides a substrate having an aluminium layer deposited thereon from a precursory decomposing same on the substrate, wherein the precursor is a tritertiary butyl aluminium.

In a preferred method of the invention the precursor is delivered to a substrate as a vapour phase and is pyrolyzed on the substrate to leave a film of metal on the substrate. The method of the invention may also be carried out in the liquid phase, such as, for example, by coating the substrate with the precursor or by dipping the substrate into the precursor, before heating to pyrolyze the precursor to leave the metal on the substrate.

In a preferred method of the invention the substrate is heated to a suitable temperature to pyrolyze the precursor. Temperatures in the range of 150°C to 400°C may be suitable, although temperatures above and below this range may also be used.

The method of the invention may be used on any suitable substrate, such as silicon or polyimide. The method of the invention may be used for the growth of aluminium/silicon alloys, which require very high temperatures to pyrolyze the silicon precursor, typically SiH₄.

The method of the invention may be used for depositing semi-conducting III-V alloys such as, for example, AlGaAs, AlInAs and AlSb and for the growth of dielectrics, such as AlN.

Tritertiarybutyl aluminium (TTBA) may also be a suitable precursor for growth of low carbon AlGaAs by reduced pressure MOVPE or by chemical beam epitaxy (CBE), in which methyl-free metalorganic precursors have been shown to be essential.

Tritertiarybutyl aluminium may extend the temperature range from which high purity aluminium can be deposited. TTBA may be used in a range of applications in the growth of conductive thin films of aluminium using LPCVD.

This invention will now be further described by means of the following Example

Example

Tritertiarybutyl aluminium was synthesised using the method described in Ann. Chem. 719 (1968)40 and the resultant colourless liquid was characterised using proton nuclear magnetic resonance (¹HNMR) and inductively coupled plasma emission spectroscopy (ICP-ES)    ¹HNMR (C₆D₆) ppm : 1.3 (s, Al-C(CH₃)₃)    ICP-ES: Al content (%) found 13.1, calculated 13.6.

Aluminium films were deposited in a simple cold wall horizontal quartz reactor (Electrogas Ltd) using radiant substrate heating. The substrates used were Si (111) single crystal slices which were degreased using acetone, washed in 20% HNO₃/Dl water and dried before use. No further pre-treatment was used. The TTBA source was held at 30°C at which temperature it has a suitable vapour pressure (&gt;lTorr) for LPCVD. This produced growth rates upto 1.2 mh^-1 at a substrate temperature of 400°C. Layer thickness was obtained using tallystep methods. A full summary of growth conditions is given in Table 1 below. <tables id="tabl0001" num="0001"><table frame="all"><title>Table 1</title><tgroup cols="2" colsep="1" rowsep="0"><colspec colnum="1" colname="col1" colwidth="78.75mm" /><colspec colnum="2" colname="col2" colwidth="78.75mm" /><thead valign="top"><row rowsep="1"><entry namest="col1" nameend="col2" align="center">Growth conditions used to deposit aluminium from TTBA</entry></row></thead><tbody valign="top"><row><entry namest="col1" nameend="col1" align="left">Cell pressure</entry><entry namest="col2" nameend="col2" align="left">4.56 Torr</entry></row><row><entry namest="col1" nameend="col1" align="left">Substrates</entry><entry namest="col2" nameend="col2" align="left">Single crystal Si(111)</entry></row><row><entry namest="col1" nameend="col1" align="left">TTBA source temperature</entry><entry namest="col2" nameend="col2" align="left">30°C</entry></row><row><entry namest="col1" nameend="col1" align="left">N₂ carrier gas flow</entry><entry namest="col2" nameend="col2" align="left">1.0S - 3.0 SCCM</entry></row><row><entry namest="col1" nameend="col1" align="left">Growth Temperature</entry><entry namest="col2" nameend="col2" align="left">300 - 400°C</entry></row><row rowsep="1"><entry namest="col1" nameend="col1" align="left">Maximum growth rates</entry><entry namest="col2" nameend="col2" align="left">1.5 mh^-1 at 400°C</entry></row></tbody></tgroup></table></tables>

The aluminium films were characterised initially by dissolution in hydrochloric acid and metals analysis for by inductively coupled mass spectrometry (ICP-MS) which showed them to be aluminium &gt; 99% purity on a metals basis.

Aluminium films were deposited from TTBA in the temperature range of from 300 400°C and were matt grey with only a low reflectivity (typically 30% at 633nm). This may be attributed to rough surface morphology which has frequently been observed in films deposited using TIBA unless pre-treatment with TiCl₄ is employed.

The aluminium films produced from TTBA were found to be conducting.

The adhesive properties of films grown on Si(111) at 400°C was also excellent and in the "Scotch tape" test the films remained intact as the tape was peeled away from the aluminium film.

The use of trialkylaluminium precursors for deposition of aluminium raises concern about incorporation of carbon in the deposited film especially at the relatively high substrate temperatures used in this Example. However, the results of Auger electron analysis, as shown in Table 2 below indicate that only trace carbon and oxygen are present in aluminium films grown at 400°C using TTBA.

For comparison the conventional precursor TIBA was used to deposit an aluminium film under identical conditions to those shown in Table 1 above. Auger analysis of this layer is given in Table 2 below and shows it to be of lower purity than the layer from TTBA, containing higher levels of carbon and of oxygen. Further analysis of separate aluminium films by secondary ion mass spectroscopy confirmed that carbon levels were at least a factor of three lower in aluminium films grown using TTBA compared with those grown using TIBA. <tables id="tabl0002" num="0002"><table frame="all"><title>Table 2</title><tgroup cols="4" colsep="1" rowsep="1"><colspec colnum="1" colname="col1" colwidth="39.37mm" /><colspec colnum="2" colname="col2" colwidth="39.37mm" /><colspec colnum="3" colname="col3" colwidth="39.37mm" /><colspec colnum="4" colname="col4" colwidth="39.37mm" /><thead valign="top"><row><entry namest="col1" nameend="col4" align="center">Auger electron spectral analysis of aluminium films grown at 400°C on Si(111) using TTBA and TIBA.</entry></row><row><entry namest="col1" nameend="col4" align="center">Atomic Composition %</entry></row><row><entry namest="col1" nameend="col1" align="left">Film Precursor</entry><entry namest="col2" nameend="col2" align="left">A1</entry><entry namest="col3" nameend="col3" align="left">C</entry><entry namest="col4" nameend="col4" align="center">O</entry></row></thead><tbody valign="top"><row rowsep="0"><entry namest="col1" nameend="col1" align="left">TTBA</entry><entry namest="col2" nameend="col2" align="left">98.2</entry><entry namest="col3" nameend="col3" align="left">0.7</entry><entry namest="col4" nameend="col4" align="char" char=".">1.1</entry></row><row><entry namest="col1" nameend="col1" align="left">TIBA</entry><entry namest="col2" nameend="col2" align="left">84.5</entry><entry namest="col3" nameend="col3" align="left">3.1</entry><entry namest="col4" nameend="col4" align="char" char=".">12.4</entry></row><row rowsep="1"><entry namest="col1" nameend="col4" align="justify">* Sub-surface information (2000 A or below) obtained by combining AES with sequential ion bombardment.</entry></row></tbody></tgroup></table></tables>

Levels of oxygen in aluminium films grown using TTBA were found to be lower than those grown using TIBA. This may reflect a reduced tendency for oxygen to be entrained in the sterically bulky and rigid TTBA molecule. The presence of oxygen at all in the TTBA-grown film may be attributed to the use of a simple CVD reactor from which rigorous exclusion of trace oxygen was not possible.