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Cleaning Gas Mixture for an Apparatus and Cleaning Method

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Cleaning Gas Mixture for an Apparatus and Cleaning Method Europäisches Patentamt *EP001529854A1* (19) European Patent Office Office européen des brevets (11) EP 1 529 854 A1 (12) EUROPEAN PATENT APPLICATION (43) Date of publication: (51) Int Cl.7: C23C 16/44, H01L 21/00 11.05.2005 Bulletin 2005/19 (21) Application number: 04256591.1 (22) Date of filing: 26.10.2004 (84) Designated Contracting States: (72) Inventors: AT BE BG CH CY CZ DE DK EE ES FI FR GB GR • Isaki, Ryuichiro, HU IE IT LI LU MC NL PL PT RO SE SI SK TR Taiyo Nippon Sanso Corporation Designated Extension States: Shinagawa-ku, Tokyo (JP) AL HR LT LV MK • Shinriki, Manabu, Taiyo Nippon Sanso Corporation (30) Priority: 04.11.2003 JP 2003374160 Shinagawa-ku, Tokyo (JP) (71) Applicant: Taiyo Nippon Sanso Corporation (74) Representative: Smyth, Gyles Darren Shinagawa-ku, Tokyo (JP) Marks & Clerk 90 Long Acre London WC2E 9RA (GB) (54) Cleaning gas mixture for an apparatus and cleaning method (57) A cleaning gas improves the etching reaction and an integer from 1 to 3, y is an integer from 1 to 12, rate of cleaning gas including a fluorocarbon gas, and and z is selected from 0 and 1 and oxygen gas, to which increases the cleaning effect. And the cleaning method is added at least one selected from the group of nitrogen uses the cleaning gas. A mixed gas of a fluorocarbon trifluoride, fluorine, nitrous oxide, nitrogen, and rare gas- gas represented by the general formula of CvHxFyOz, es up to 10% by volume based on the total gas volume. wherein v is an integer from 1 to 5, x is selected from 0 EP 1 529 854 A1 Printed by Jouve, 75001 PARIS (FR) 1 EP 1 529 854 A1 2 Description ciency since these are raw materials for producing fluor- ocarbon type resins such as TEFLON (trademark), and BACKGROUND OF THE INVENTION are used in significantly large amounts in the chemical industry. Field of the Invention 5 [0006] However, since these fluorocarbon gases which are short-lived in the atmosphere are easily po- [0001] The present invention relates to a cleaning gas lymerized, these gases cause a problem in that the etch- and to a cleaning method. In particular, the present in- ing rate generally decreases during cleaning of silicon vention relates to a cleaning gas composition for dry oxide films, etc. Decreasing the etching rate causes cleaning to remove deposits such as silicon oxide films 10 problems in the removal times and in the removal effi- which has formed inside a semiconductor film forming ciency of deposits inside the chamber in the cleaning device such as an apparatus for producing semiconduc- process, and it is necessary to reduce the time so as to tor devices, an offline surface modifying device, and a maintain the process efficiency. thin film forming apparatus, and relates to a cleaning [0007] Objects of the present invention are to provide method using the cleaning gas. 15 a cleaning gas including fluorocarbon gas which in- [0002] Priority is claimed on Japanese Patent Appli- creases the speed of etching reactions and increases cation No. 2003-374160, filed November 4, 2003, the the cleaning efficiency, and a cleaning method using the content of which is incorporated herein by reference. cleaning gas. [0008] A cleaning gas of the present invention to Description of Related Art 20 achieve the object is a cleaning gas to remove deposits accumulated inside a semiconductor film forming de- [0003] A dry cleaning method may be used to remove vice, and which includes a mixed gas containing a fluor- (etch off) deposits by introducing a cleaning gas includ- ocarbon gas, having at least one double bond per mol- ing fluorocarbon gases into a processing chamber and ecule, represented by the general formula generating plasma in the processing chamber to re- 25 move deposits, for example, silicon oxide accumulated CvHxFyOz inside the chamber inside a semiconductor film forming device such as an apparatus for producing semiconduc- tor devices, an offline surface modifying device, and a wherein v is an integer from 1 to 5, x is selected from 0 thin film forming apparatus. The cleaning gas used in 30 and an integer from 1 to 3, y is an integer from 1 to 12, these steps, may be fluorocarbon gas alone, but is usu- and z is selected from 0 and 1; oxygen; and at least one ally fluorocarbon gas diluted with oxygen or rare gases selected from the group of nitrogen trifluoride, fluorine, 10 to 30 times (see for example Japanese Patent No. nitrous oxide, nitrogen, and rare gases up to 10 % by 2904723). volume based on the total gas volume. 35 [0009] A cleaning method of the present invention is SUMMARY OF THE INVENTION a method to remove deposits accumulated inside a semiconductor film forming device, which includes a [0004] Decreasing the quantity of fluorocarbon gases step of introducing a cleaning gas including a mixed gas consumed, and decomposition and removal after use of containing a fluorocarbon gas represented by the gen- fluorocarbon gases in processes are needed since 40 eral formula many fluorocarbon gases have extremely high Global Warming Potential (GWP). Efficient ways of using fluor- CvHxFyOz ocarbon gases, which further decrease the quantity con- sumed, are needed which maintain process perform- ance. On the other hand, it is known that the GWP of 45 wherein v is an integer from 1 to 5, x is selected from 0 unsaturated fluorocarbon gas having double bond per and an integer from 1 to 3, y is an integer from 1 to 12, molecule or a composition having an oxygen atom per and z is selected from 0 and 1; oxygen; and at least one molecule in a type of fluorocarbon gas becomes sub- selected from the group of nitrogen trifluoride, fluorine, stantially less than that of saturated fluorocarbon gases nitrous oxide, nitrogen, and rare gases up to 10 % by since unsaturated fluorocarbon gases having at least 50 volume based on the total gas volume in the semicon- one double bond per molecule or a composition having ductor film forming device; and a step of plasma excita- an oxygen per molecule are decomposed rapidly after tion of the cleaning gas by exposure to high frequency release to the atmosphere. electromagnetic radiation. [0005] These fluorocarbon gases which are short- [0010] By the present invention, removal of the de- 55 lived in the atmosphere are represented by C2F4,C3F6, posits such as silicon oxide film accumulated inside a and C3F6O, and these gases are obtainable without new semiconductor film forming device at a high rate while methods of synthesis of gases for the semiconductor suppressing the release of the global warming sub- processes and these have advantages in energy effi- stances is possible. 2 3 EP 1 529 854 A1 4 [0011] The present invention increases the efficiency are considered to generally have a low etching rate; of use of the semiconductor film forming device since however, the etching rate can be increased by supplying the present invention efficiently cleans off deposits such radicals to the reaction environment which radicals react as silicon oxide accumulated inside the semiconductor by addition reaction to the double bond per molecule. film forming device such as an apparatus for producing 5 The double bond of the unsaturated fluorocarbon mol- semiconductor devices, an offline surface modifying de- ecule has a high bond dissociation energy even though vice, and a thin film forming apparatus. it has a low decomposition efficiency in plasma, and the chemical reactivity is high and reacts with various radi- BRIEF DESCRIPTION OF THE DRAWINGS cals at an extremely high rate. Applying these proper- 10 ties, the reaction environment which easily generates [0012] active species which contribute to the etching reaction can be obtained by adding gas having a reaction assist FIG. 1 is a graph showing the bond dissociation en- action to minimize the effect on the entire process. Fur- ergy of each gas; thermore, an effective plasma can be generated rapidly FIG. 2 is a graph showing the relationship between 15 and the higher density active species can be produced the concentration of nitrogen trifluoride and the by adding small quantities of gases of low breakdown etching rate in Comparative Example 1; voltage. FIG 3 is a graph showing the relationship between [0015] When these kinds of fluorocarbon gases are the concentration of fluorocarbon gas and the etch- used as cleaning gases, mixed gases of these fluoro- ing rate in Comparative Example 2; 20 carbon gases and oxygen gas are added with small FIG. 4 is a graph showing the relationship between quantities of gases having an action to increase the the addition amount of nitrogen trifluoride and the cleaning rate (or the etching rate) (which is the reaction etching rate in Example 1; assist action). The mixing ratio of fluorocarbon gases FIG. 5 is a graph showing the relationship between and oxygen gas is optional and the mixing ratio can be the addition amount of nitrous oxide and the etching 25 set properly depending on the type of the fluorocarbon rate in Example 2; gas. FIG. 6 is a graph showing the relationship between [0016] The addition gases having a reaction assist ac- the addition amount of nitrogen and argon, and the tion indicates gases which easily generate radicals in etching rate in Example 3; plasma and gases having low breakdown voltage, and FIG. 7 is a graph showing collectively the increasing 30 the gases which easily generate radicals in plasma in- ratio of etching rate when each of the additive gases dicate gases which easily generate F radicals, O radi- is added in amounts of 10% by volume respectively; cals, and N radicals contributing to the etching reaction, and specifically nitrogen trifluoride, fluorine, nitrous oxide, FIG.
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