A PROCESS FOR PRODUCING A HIGH PURITY OXIDE LAYER ON A SEMICONDUCTOR SUBSTRATE

Abstract: A high purity oxide layer is produced on a semiconductor substrate (8) by heating the substrate in the presence of an oxidising ambient in a multi-walled reaction chamber (1) provided with a heating element (12). Simultaneously a halogen-containing ambient is caused to flow through an outer portion (10) of the reaction chamber. A gaseous ambient is caused to flow through an intermediate portion (9) of the reaction chamber to remove water by-product from the reaction with the halogen which occurs in the outer portion (10) of the reaction chamber.

Description: The present invention relates to a process for producing a high purity oxide layer on a semiconductor substrate. In the fabrication of semiconductor devices it is often necessary to provide an insulating oxide layer on a semiconductor substrate. One way in which the oxide layer is formed is by heating the substrate in an oxidising atmosphere in a reaction chamber for a time and at a temperature sufficient to provide the desired oxide layer. One problem associated with high-temperature oxidation of semiconductor substrates is the contamination of the oxide with impurities occurring in the oxidising ambient including those metal impurities which diffuse from the furnace heating the ambient through the walls of the reaction chamber. It is known that contamination of the semiconductor substrate with alkali metals and transition metals can be harmful. Such harmful effects caused by various alkali metal contaminants and/or transition metal contaminants include degradation of minority carrier lifetimes; increase of junction leakages; and shifts in the flat band voltage. It has been suggested in GB-A-2082384 to provide an HC1 protective atmosphere in an outer chamber around the reaction chamber in order to remove metal contaminants. However, that technique has not been entirely satisfactory since it has been found that there is a tendency for some contamination to occur due to water or moisture associated with the halogen ambient or reaction products with the halogen. The present invention seeks to provide a process which results in less contamination of the oxide layer. It provides a process for producing a high purity oxide layer on a semiconductor substrate, the process comprising performing the following operations simultaneously: (a) heating a substrate disposed inside the inner wall of a triple-walled reaction chamber having spaced inner, intermediate and outer walls; (b) directing an oxidising ambient over the substrate; (c) passing a halogen-containing ambient through the space between the outer and intermediate walls of the chamber; and (d) passing a water-removing gaseous ambient through the space between the intermediate and the inner walls of the chamber. How the invention can be carried out will now be described way of example, with reference to the accompanying drawing which is a schematic diagram of reaction chamber apparatus. With reference to the drawing, a triple-walled reaction chamber 1 is in the form of an annular tube which preferably is constructed of high purity vitreous silica. The high purity vitreous silica tube includes an inner cylindrical wall portion 2, an outer cylindrical wall portion 4, and an intermediate cylindrical wall portion 3. Inner wall portion 2 contains openings at 5 and 6 at each end, respectively, and defines a core section 7. In core section 7 are inserted semiconductor substrates 8 which are to be exposed to an oxidising ambient. Preferred substrates are silicon wafers. The wafers are suitably supported so as to expose their major surfaces to be oxidised. Intermediate wall portion 3 includes a closure at each end with the inner wall portion 2 whereby there is formed an annular section 9 which is completely isolated from the reaction chamber section 7 by the inner wall portion 2. Outer wall portion 4 includes a closure at each end with intermediate wall portion 3 whereby there is formed an annular section 10 which is completely isolated from intermediate portion 9 by the intermediate wall portion 3. Typical dimensions include an interior diameter of about 5 cm to about 25 cm for the inner core section; a separation of about 1 to about 2 centimetres between the two walls in the intermediate annular section; and about 1 to about 2 centimetres between the two walls along the annular outer tabular section. Wall thicknesses of about 2 to about 5 millimetres and a length of about 1.3 metres to about 3 metres are typical. Surrounding the reaction chamber 1 is a liner 11, such as aluminum silicate ceramic such as available under the trade designation Mullite; alumina; or zirconia. The liner 11 is used to smooth-out the temperature profile and to shield the quartz tube from the resistive heater winding 12 which is supported in slots in the heater support ceramic member 13. The liner is not necessary, but only desirable, and the outer and intermediate wall portion can adequately serve the function of the liner. In addition, provision is made to provide a heating current (not shown) to the winding 12. Also not shown are the various thermo-couples that would be or could be included as part of the temperature controls. An oxidising agent is caused to flow longitudinally through the inner core section and past the substrates, the oxidising agent entering via opening 5 and leaving through opening 6. The oxidising agent is preferably dry oxygen gas and/or dry gas mixtures which contain oxygen such as dry air and dry mixtures with diluent gases such as nitrogen and argon. When mixtures containing oxygen are employed, they should include at least about 10% and preferably at least about 20% by volume of oxygen. The dry gas should be substantially water free and typically contain about 10 ppm or less and preferably about 1 ppm or less of water. To ensure that the oxidising gas is dry and as pure as possible, it may be desirable to pass the gas through a molecular sieve filter, followed by heating in an oven at about 900°C to burn off any organic materials which might be present, and then pass the gas through a trap at about -80°C to remove water which might still be present. The wafers are usually maintained at a temperature of about 800°C to about 1200°C and preferably about 900°C to about 1100°C to achieve the oxidation, a typical temperature being about 1000°C. Normally, the oxidation takes about 15 minutes to about 3 hours and preferably about ½ hour to about 1 hour to provide an oxide thickness of about 10 nm to about 100 nm at about 1000°C. The oxidising agent is provided at a flow rate of about 1 to about 5 litres/minute for a reaction chamber wherein the inner core section has an interior diameter of about 7.5 to 10 cm and is about 2.1 metres long. A halogen-containing ambient is caused to flow through the outer annular tube, entering through inlet 14 and leaving via outlet 15. Any gas mixture capable of providing halogen at the required temperature can be employed. Examples of such gas mixtures are HC1 in dry oxygen and chlorinated hydrocarbons in dry oxygen. Typical chlorinated hydrocarbons include 1,1,1 trichloroethane; 1,1,2 trichloroethane, trichloroethylene, and carbon tetrachloride; preferred of which is 1,1,1, trichloroethane. In general, the gas mixture contains about 1 to 10% by volume of the halogen and about 90 to 99% by volume of the oxygen, typically about 5% by volume of the halogen and about 95% by volume of the oxygen. Of course, mixtures of halogens with the oxygen can be used, if desired. At the temperatures of about 800°C to about 1100°C, typically about 1000°C, C1₂ and/or flash HC1 is formed. The chlorine and/or flash HC1 gas then reacts with any alkali metal or transition metal or other metal that indiffuses from the furnace to thereby form volatile metal halides. These volatile metal halides are then removed from the outer annular tube by the flowing oxygen-containing gas, thereby precluding these metals from diffusing into the inner annular tube and the oxidation tube. The gas mixture is introduced at a rate of about 500cc/minute to about 1500cc/minute, typically about 750 cc/minute. Through the intermediate annular tube is caused to flow gas for removal of any water-by-product from the outer annular tube. The gas flows in through inlet 16 and out through outlet 17. The flow rate is about 500 cc/minute to about 1500 cc/minute, typically about 750 cc/minute. The preferred gases are dry air, dry oxygen, and dry nitrogen and mixtures thereof. These gases are usually at temperatures of about 800°C to about 1100°C, typically about 1000°C. These gases need not be quite as dry as the oxidation gases or oxygen used with the halogen, but desirably should be of high purity and typically contain 10 ppm of water or less. To ensure the desired degree of dryness, the gas to be employed can be passed through a molecular sieve followed by being passed through a trap at about -80°C. The gas employed prevents water, which is produced from the reaction of the halogen-containing compound with the oxygen to form the chlorine in the outer annular tube, from diffusing into the oxidation tube. This ensures a dry oxidation process. In a typical example, silicon waters are placed in a reaction chamber having an inner core section with an interior diameter of about 7.5 to 10 cm and about 2.1 metres long. The wafers are heated to a temperature of 1000°C. Dry oxygen gas is passed through the chamber at a rate of about 1 to about 5 litres/minute for about 1 hour. At the same time, a mixture of about 5% by volume of 1,1,1 trichloroethane and about 95% by volume of oxygen is passed through the outer tubular section at a temperature of about 1000°C at a rate of about 750 cc/minute. Also at the same time dry oxygen is passed through the intermediate annular tube at a temperature of about 1000°C at a rate of about 750 cc/minute. Wafers so treated were tested for breakdown voltage field failure and demonstrated improved results. Typically, the breakdown voltage field is about 9 x 10⁶ volts/cm with few low voltage breakdowns. The values obtained were relatively closely distributed.

Claims: A process for producing a high purity oxide layer on a semiconductor substrate, the process comprising performing the following operations simultaneously: (a) heating a substrate (8) disposed inside the inner wall (2) of a triple-walled reaction chamber having spaced inner, intermediate and outer walls (2,3,4); (b) directing an oxidising ambient over the substrate; (c) passing a halogen-containing ambient through the space between the outer (4) and intermediate (3) walls of the chamber; and (d) passing a water-removing gaseous ambient through the space between the intermediate (3) and the inner (2) walls of the chamber. A process as claimed in claim 1, wherein the substrate is heated to a temperature of about 800°C to about 1200°C. A process as claimed in claim 2, wherein the substrate is heated to a temperature of about 900°C to about 1100°C. A process as claimed in claim 3, wherein the substrate is heated to a temperature of about 1000°C. A process as claimed in any preceding claim, wherein said oxidising ambient is a dry oxygen containing gas. A process as claimed in claim 5, wherein said dry oxygen containing gas is dry oxygen. A process as claimed in claim 5, wherein said dry oxygen containing gas is a mixture of dry oxygen with a diluent gas. A process as claimed in claim 7, wherein said mixture is dry air. A process as claimed in claim 7, wherein said diluent gas is nitrogen or argon. A process as claimed in any preceding claim, wherein said halogen containing ambient is at a temperature of about 800°C to 1100°C. A process as claimed in claim 10, wherein said halogen containing ambient is at a temperature of about 1000°C. A process as claimed in any preceding claim, wherein said halogen containing ambient is a mixture of dry oxygen and a halogen containing gas. A process as claimed in claim 12, wherein said halogen containing gas is HC1 or a chlorinated hydrocarbon. A process as claimed in claim 12 or claim 13, wherein said halogen containing ambient contains about 90% to about 99% by volume of oxygen and about 1% to about 10% by volume of said halogen containing gas. A process as claimed in claim 14, wherein said halogen containing gas is 1,1,1 trichloroethane. A process as claimed in any preceding claim, wherein substrate is a silicon substrate. A process as claimed in any preceding claim, wherein said water-removing gaseous ambient is dry air, dry oxygen, or dry nitrogen. A process as claimed in any preceding claim, wherein said water-removing gaseous ambient is at a temperature of about 800°C to 1100°C. A process as claimed in claim 18, wherein said water-removing gaseous ambient is at a temperature of about 1000°C.

Inventors: BLUM, SAMUEL EMIL
Applicants: INTERNATIONAL BUSINESS MACHINES CORPORATION
Application year: 1986
Main classification: H01L21
IPC codes: H01L21