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US20050211375A1 - Method of manufacturing a semiconductor device - Google Patents

Method of manufacturing a semiconductor device Download PDF

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Publication number
US20050211375A1
US20050211375A1 US11/096,125 US9612505A US2005211375A1 US 20050211375 A1 US20050211375 A1 US 20050211375A1 US 9612505 A US9612505 A US 9612505A US 2005211375 A1 US2005211375 A1 US 2005211375A1
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Prior art keywords
silicon
recited
aqueous solution
nitrogen containing
containing material
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US11/096,125
Inventor
Dirk Knotter
Johannes Van Wingerden
Madelon Rovers
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NXP BV
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Individual
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Priority to US11/096,125 priority Critical patent/US20050211375A1/en
Publication of US20050211375A1 publication Critical patent/US20050211375A1/en
Assigned to NXP B.V. reassignment NXP B.V. ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: KONINKLIJKE PHILIPS ELECTRONICS N.V.
Abandoned legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K13/00—Etching, surface-brightening or pickling compositions
    • C09K13/04—Etching, surface-brightening or pickling compositions containing an inorganic acid
    • C09K13/08—Etching, surface-brightening or pickling compositions containing an inorganic acid containing a fluorine compound
    • H10P50/613—
    • H10P50/283—
    • H10P76/2043—
    • H10P72/0422—
    • H10P72/0426—

Definitions

  • the invention relates to a method of manufacturing a semiconductor device comprising the step of removing a silicon and nitrogen containing material by means of wet etching.
  • Silicon and nitrogen containing materials such as silicon nitride and silicon oxynitride, are frequently used in the manufacture of integrated circuits.
  • One application of such a material consists in using it as a bottom antireflective coating (BARC) to better control the critical dimension (CD) of the gate as defined via a resist mask formed thereon.
  • the wafer stack may comprise a gate oxide layer over a semiconductor substrate, a polysilicon layer over the gate oxide layer, a BARC over the conductive layer, and a resist mask over the BARC.
  • the wafer stack is then shaped to form one or more polysilicon gates by sequentially etching through selected portions of the BARC and the gate conductive layer as defined by the etch windows in the resist mask.
  • silicon and nitrogen containing materials such as silicon nitride and silicon oxynitride, is not limited to the above-indicated examples, but that many other applications exist.
  • wet etching of such a material is often carried out in hot phosphoric acid at a high operational temperature, usually a temperature between 140° C. and 180° C., which etching process enables a high selectivity with respect to silicon oxide and silicon oxide like materials.
  • this high selectivity is meant that the silicon and nitrogen containing material is etched at a rate significantly greater than that of silicon oxide or a silicon oxide like material
  • an organic photoresist is not resistant to the high temperatures and is removed during the etching process, 2) the etching process is prone to particle contamination, 3) the selectivity to exposed polylines is poor, 4) the selectivity to exposed silicon oxide or an exposed silicon oxide like material is dependent on the age of the bath; the selectivity of a fresh bath can be considerably lower than the selectivity of an old bath, 5) the process time needed for etching is quite long which makes the etching process suitable for multi-wafer processes only, that is processes wherein multiple wafers are simultaneously processed in one and the same process chamber.
  • An alternative is to wet etch a silicon and nitrogen containing material, such as silicon nitride or silicon oxynitride, in a dilute aqueous hydrofluoric acid (HF) solution having a hydrofluoric acid concentration in the range from about 0.001 M to about 0.1 M at an operational temperature between 25° C. and 90° C.
  • HF dilute aqueous hydrofluoric acid
  • the temperature and the hydrofluoric acid concentration cannot be tuned in the above-indicated ranges so that the etch rate becomes high enough for the etching process to be efficiently carried out by means of a single-wafer process without negatively affecting the etch selectivity with respect to silicon oxide or a silicon oxide like material.
  • the invention has inter alia for its object to provide a method of the kind mentioned in the opening paragraph, in which method the performance of the step of removing the silicon and nitrogen containing material by means of wet etching is improved.
  • the step of removing the silicon and nitrogen containing material by means of wet etching of the method according to the invention is for this purpose carried out with an aqueous solution comprising hydrofluoric acid in a low concentration, the aqueous solution being applied under elevated pressure to reach a temperature above 100° C.
  • an aqueous solution comprising hydrofluoric acid in a low concentration
  • the aqueous solution being applied under elevated pressure to reach a temperature above 100° C.
  • the temperature of the aqueous solution can be raised to above 100° C., which increases the etch rate in such a way that the etching process can be carried out fast enough by means of a single-wafer process.
  • a temperature of above 100° C. does not negatively affect the etch selectivity with respect to silicon oxide or a silicon oxide like material. On the contrary, this etch selectivity is even increased.
  • the process of etching the silicon and nitrogen containing material can be carried out by means of a multi-wafer process in e.g. a spray tool or a wet bench.
  • a multi-wafer wafer process is a process, in which multiple wafers are simultaneously processed in one and the same process chamber.
  • the process of etching the silicon and nitrogen containing material can also be advantageously carried out by means of a single-wafer process, i.e. a process in which just one wafer is processed in one and the same process chamber at a time.
  • the invention further relates to an apparatus for carrying out the step of removing a silicon and nitrogen containing material by means of etching with an aqueous solution comprising hydrofluoric acid in a low concentration, the aqueous solution being applied under elevated pressure to reach a temperature above 100° C.
  • FIGS. 1 to 4 show in diagrammatic cross-sectional views successive stages in the manufacture of a semiconductor device using the method in accordance with the invention.
  • FIG. 1 shows a substrate 1 , which consists of a semiconductor body, for example a silicon body, provided with a layer of a dielectric material 2 as uppermost layer. It will be clear to a person skilled in the art that, dependent on the stage of the manufacturing process, the substrate 1 can consist of other layers and structures in addition.
  • a layer of silicon 3 On the layer of dielectric material 2 there is a layer of silicon 3 .
  • the layer of silicon 3 which in the present example is applied as a gate layer, is advantageously applied as a layer of polycrystalline silicon or amorphous silicon.
  • an inorganic anti-reflective layer 4 of a silicon and nitrogen containing material is applied, which silicon and nitrogen containing material is preferably silicon nitride or silicon oxynitride, and even more preferably silicon-rich silicon nitride or silicon-rich silicon oxynitride.
  • the layer of dielectric material 2 which is applied as gate dielectric layer in the present example, is advantageously composed of a material with respect to which the inorganic anti-reflective layer ( 4 ) of the silicon and nitrogen containing material can be selectively etched, such as silicon oxide or a silicon oxide like material.
  • the inorganic anti-reflective layer 4 is provided with a resist mask 6 .
  • the inorganic anti-reflective layer 4 is patterned by means of the resist mask 6 in a usual way. Then, the resist mask 6 is removed in a usual way ( FIG. 2 ).
  • the layer of silicon 3 is patterned in a usual way down to the layer of dielectric material 2 by means of etching while using the patterned inorganic anti-reflective layer 4 as a hard mask.
  • the inorganic anti-reflective layer 4 of the silicon and nitrogen containing material is removed by means of etching with an aqueous solution comprising hydrofluoric acid in a low concentration, preferably a concentration in the range from about 0.001 to 0.1 M.
  • the aqueous solution is applied at a temperature above 100° C., preferably a temperature in the range from 100° C. to 130° C.
  • the temperature of the aqueous solution can be increased to a value above 100° C. by using the aqueous solution at elevated pressure.
  • Another way of accomplishing the above may be by heating up the aqueous solution to the desired temperature in a closed airtight system. During this heating-up the pressure inside the closed airtight system rises which in turn causes an increase in the temperature of the aqueous solution that can be ultimately reached.
  • a still further way may be by using a hydraulic pump.
  • attack of the exposed sidewalls of the layer of silicon 3 is counteracted.
  • the inorganic anti-reflective layer 4 can be removed without any important change occurring in the critical dimension (CD).
  • attack of this top wall is also counteracted during the above-mentioned etching process.
  • this etching process in addition has a good selectivity with respect to the layer of dielectric material 2 , that is the inorganic anti-reflective layer 4 is etched at a rate significantly greater than that of the layer of dielectric material 2 . The higher the temperature in the range from 100° C.

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  • Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Weting (AREA)
  • Insulated Gate Type Field-Effect Transistor (AREA)
  • Drying Of Semiconductors (AREA)
  • Internal Circuitry In Semiconductor Integrated Circuit Devices (AREA)
  • ing And Chemical Polishing (AREA)
  • Electrodes Of Semiconductors (AREA)

Abstract

The invention relates to a method of manufacturing a semiconductor device comprising the step of removing a silicon and nitrogen containing material by means of wet etching with an aqueous solution comprising hydrofluoric acid in a low concentration, the aqueous solution being applied under elevated pressure to reach a temperature above 100° C.

Description

  • The invention relates to a method of manufacturing a semiconductor device comprising the step of removing a silicon and nitrogen containing material by means of wet etching.
  • Silicon and nitrogen containing materials, such as silicon nitride and silicon oxynitride, are frequently used in the manufacture of integrated circuits. One application of such a material consists in using it as a bottom antireflective coating (BARC) to better control the critical dimension (CD) of the gate as defined via a resist mask formed thereon. The wafer stack may comprise a gate oxide layer over a semiconductor substrate, a polysilicon layer over the gate oxide layer, a BARC over the conductive layer, and a resist mask over the BARC. The wafer stack is then shaped to form one or more polysilicon gates by sequentially etching through selected portions of the BARC and the gate conductive layer as defined by the etch windows in the resist mask. Once properly shaped, the remaining portions of the resist mask and BARC are removed. During removal of the BARC by means of wet etching the sidewalls of the polysilicon gate(s) as well as the non-covered portions of the gate oxide layer are exposed to the etch mixture used for wet etching the BARC. Another application of such a material consists in using it as mask in the so-called shallow trench isolation (STI) process, wherein during removal of this mask by means of wet etching the field oxide regions are exposed to the etch mixture applied. It will be clear to a person skilled in the art of manufacturing processes for integrated circuits that the application of silicon and nitrogen containing materials, such as silicon nitride and silicon oxynitride, is not limited to the above-indicated examples, but that many other applications exist.
  • Wet etching of such a material is often carried out in hot phosphoric acid at a high operational temperature, usually a temperature between 140° C. and 180° C., which etching process enables a high selectivity with respect to silicon oxide and silicon oxide like materials. By this high selectivity is meant that the silicon and nitrogen containing material is etched at a rate significantly greater than that of silicon oxide or a silicon oxide like material However, several problems are coupled to this etching process: 1) an organic photoresist is not resistant to the high temperatures and is removed during the etching process, 2) the etching process is prone to particle contamination, 3) the selectivity to exposed polylines is poor, 4) the selectivity to exposed silicon oxide or an exposed silicon oxide like material is dependent on the age of the bath; the selectivity of a fresh bath can be considerably lower than the selectivity of an old bath, 5) the process time needed for etching is quite long which makes the etching process suitable for multi-wafer processes only, that is processes wherein multiple wafers are simultaneously processed in one and the same process chamber.
  • An alternative is to wet etch a silicon and nitrogen containing material, such as silicon nitride or silicon oxynitride, in a dilute aqueous hydrofluoric acid (HF) solution having a hydrofluoric acid concentration in the range from about 0.001 M to about 0.1 M at an operational temperature between 25° C. and 90° C. Most of the problems coupled to the etching process with hot phosphoric acid are solved by using a dilute aqueous hydrofluoric acid solution in the above temperature range. However, one important problem still remains. The temperature and the hydrofluoric acid concentration cannot be tuned in the above-indicated ranges so that the etch rate becomes high enough for the etching process to be efficiently carried out by means of a single-wafer process without negatively affecting the etch selectivity with respect to silicon oxide or a silicon oxide like material.
  • The invention has inter alia for its object to provide a method of the kind mentioned in the opening paragraph, in which method the performance of the step of removing the silicon and nitrogen containing material by means of wet etching is improved.
  • The step of removing the silicon and nitrogen containing material by means of wet etching of the method according to the invention is for this purpose carried out with an aqueous solution comprising hydrofluoric acid in a low concentration, the aqueous solution being applied under elevated pressure to reach a temperature above 100° C. By applying the aqueous solution at elevated pressure the temperature of the aqueous solution can be raised to above 100° C., which increases the etch rate in such a way that the etching process can be carried out fast enough by means of a single-wafer process. In addition, a temperature of above 100° C. does not negatively affect the etch selectivity with respect to silicon oxide or a silicon oxide like material. On the contrary, this etch selectivity is even increased.
  • The process of etching the silicon and nitrogen containing material can be carried out by means of a multi-wafer process in e.g. a spray tool or a wet bench. A multi-wafer wafer process is a process, in which multiple wafers are simultaneously processed in one and the same process chamber. However, as the method according to the invention enables etch rates that are significantly higher than that of prior art methods, the process of etching the silicon and nitrogen containing material can also be advantageously carried out by means of a single-wafer process, i.e. a process in which just one wafer is processed in one and the same process chamber at a time.
  • Further advantageous embodiments of the method in accordance with the invention are described in the dependent claims.
  • The invention further relates to an apparatus for carrying out the step of removing a silicon and nitrogen containing material by means of etching with an aqueous solution comprising hydrofluoric acid in a low concentration, the aqueous solution being applied under elevated pressure to reach a temperature above 100° C.
  • These and other aspects of the invention will be explained in more detail with reference to the drawing, in which
  • FIGS. 1 to 4 show in diagrammatic cross-sectional views successive stages in the manufacture of a semiconductor device using the method in accordance with the invention.
  • FIG. 1 shows a substrate 1, which consists of a semiconductor body, for example a silicon body, provided with a layer of a dielectric material 2 as uppermost layer. It will be clear to a person skilled in the art that, dependent on the stage of the manufacturing process, the substrate 1 can consist of other layers and structures in addition. On the layer of dielectric material 2 there is a layer of silicon 3. The layer of silicon 3, which in the present example is applied as a gate layer, is advantageously applied as a layer of polycrystalline silicon or amorphous silicon. On the layer of silicon 3 an inorganic anti-reflective layer 4 of a silicon and nitrogen containing material is applied, which silicon and nitrogen containing material is preferably silicon nitride or silicon oxynitride, and even more preferably silicon-rich silicon nitride or silicon-rich silicon oxynitride. The layer of dielectric material 2, which is applied as gate dielectric layer in the present example, is advantageously composed of a material with respect to which the inorganic anti-reflective layer (4) of the silicon and nitrogen containing material can be selectively etched, such as silicon oxide or a silicon oxide like material. The inorganic anti-reflective layer 4 is provided with a resist mask 6. In between the inorganic anti-reflective layer 4 and the resist mask 6 another layer such as, for example, a silicon oxide layer may be present The inorganic anti-reflective layer 4 is patterned by means of the resist mask 6 in a usual way. Then, the resist mask 6 is removed in a usual way (FIG. 2).
  • In FIG. 3, the layer of silicon 3 is patterned in a usual way down to the layer of dielectric material 2 by means of etching while using the patterned inorganic anti-reflective layer 4 as a hard mask.
  • In FIG. 4, the inorganic anti-reflective layer 4 of the silicon and nitrogen containing material, such as silicon nitride or silicon oxynitride, is removed by means of etching with an aqueous solution comprising hydrofluoric acid in a low concentration, preferably a concentration in the range from about 0.001 to 0.1 M. The aqueous solution is applied at a temperature above 100° C., preferably a temperature in the range from 100° C. to 130° C. The temperature of the aqueous solution can be increased to a value above 100° C. by using the aqueous solution at elevated pressure. This can be accomplished, for example, by delivering a pressurized inert gas into the process chamber wherein etching of the inorganic anti-reflective layer of the silicon and nitrogen containing material is carried out. Another way of accomplishing the above may be by heating up the aqueous solution to the desired temperature in a closed airtight system. During this heating-up the pressure inside the closed airtight system rises which in turn causes an increase in the temperature of the aqueous solution that can be ultimately reached. A still further way may be by using a hydraulic pump.
  • By means of this etching process attack of the exposed sidewalls of the layer of silicon 3 is counteracted. As a result, the inorganic anti-reflective layer 4 can be removed without any important change occurring in the critical dimension (CD). Moreover, once the top wall of the layer of silicon 3 is exposed, attack of this top wall is also counteracted during the above-mentioned etching process. Furthermore, this etching process in addition has a good selectivity with respect to the layer of dielectric material 2, that is the inorganic anti-reflective layer 4 is etched at a rate significantly greater than that of the layer of dielectric material 2. The higher the temperature in the range from 100° C. to 130° C., the higher the etch rate of the inorganic anti-reflective layer 3 and the higher the etch selectivity with respect to the layer of dielectric material 2. Moreover, in order to improve the etch selectivity between the inorganic anti-reflective layer 4 and the layer of silicon 3, i.e. to reduce the etch rate of the layer of silicon 3 relative to that of the inorganic anti-reflective layer 4, it is preferred to treat the aqueous solution in such a way that the layer of silicon 3 is kept in an non-oxidized.

Claims (13)

1-10. (canceled)
11. An apparatus for carrying out the step of removing silicon and nitrogen containing material by wet etching with an aqueous solution comprising hydrofluoric acid in a low concentration, the aqueous solution being applied under elevated pressure to reach a temperature about 100° C.
12. An apparatus for wet etching silicon and nitrogen containing material from a substrate, the apparatus comprising:
a process chamber, the process chamber being arranged as a closed airtight system, wherein etching of the silicon and nitrogen containing material occurs in an aqueous solution;
a source of heat to set the temperature of the aqueous solution to a predetermined temperature; and
a source of pressurized inert gas to elevate the pressure of the process chamber, the pressure increasing the predetermined temperature.
13. The apparatus as recited in claim 12, wherein the silicon and nitrogen containing material is silicon nitride or silicon oxynitride.
14. The apparatus as recited in claim 12, wherein the silicon and nitrogen containing material is silicon-rich silicon nitride or silicon-rich silicon oxynitride.
15. The apparatus as recited in claim 12, wherein the aqueous solution comprises hydrofluoric acid in a low concentration.
16. The apparatus as recited in claim 15, wherein the concentration of the hydrofluoric acid is in a range from about 0.001M to about 0.1M.
16. The apparatus as recited in claim 15, wherein the predetermined temperature is above 100° C.
17. The apparatus as recited in claim 16, wherein the pressure increasing the predetermined temperate, raises the predetermined temperature from above 100° C. to about 130° C.
18. The apparatus as recited in claim 12, wherein the source of pressurized inert gas is delivered using a hydraulic pump.
19. The apparatus as recited in claim 12, wherein the process chamber is configured for multiple-wafer processing or single-wafer processing.
20. The apparatus as recited in claim 12, wherein the process chamber includes a system for evacuating the aqueous solution so that dissolved oxygen is removed.
21. The apparatus as recited in claim 20, wherein the system for evacuating the aqueous solution removes dissolved oxygen by exchanging the dissolved oxygen with an inert gas.
US11/096,125 2001-04-27 2005-03-30 Method of manufacturing a semiconductor device Abandoned US20050211375A1 (en)

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PCT/IB2002/001412 WO2002089193A1 (en) 2001-04-27 2002-04-18 Method of wet etching a silicon and nitrogen containing material
US10/475,874 US6887796B2 (en) 2001-04-27 2002-04-18 Method of wet etching a silicon and nitrogen containing material
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US20090081840A1 (en) * 2007-09-20 2009-03-26 Samsung Electronics Co., Ltd. Method of Forming Field Effect Transistors Using Diluted Hydrofluoric Acid to Remove Sacrificial Nitride Spacers
US20090146296A1 (en) * 2007-12-11 2009-06-11 Chartered Semiconductor Manufacturing, Ltd. Method of forming high-k dielectric stop layer for contact hole opening
US20110076623A1 (en) * 2009-09-29 2011-03-31 Tokyo Electron Limited Method for reworking silicon-containing arc layers on a substrate

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US8268735B2 (en) * 2006-02-01 2012-09-18 Tohoku University Semiconductor device manufacturing method and method for reducing microroughness of semiconductor surface
JP5913869B2 (en) 2011-08-31 2016-04-27 林純薬工業株式会社 Etching solution composition and etching method
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TWI558850B (en) 2014-03-29 2016-11-21 精密聚合物股份有限公司 Processing liquid for electronic parts and method of manufacturing electronic parts

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US20090081840A1 (en) * 2007-09-20 2009-03-26 Samsung Electronics Co., Ltd. Method of Forming Field Effect Transistors Using Diluted Hydrofluoric Acid to Remove Sacrificial Nitride Spacers
US7902082B2 (en) 2007-09-20 2011-03-08 Samsung Electronics Co., Ltd. Method of forming field effect transistors using diluted hydrofluoric acid to remove sacrificial nitride spacers
US20090146296A1 (en) * 2007-12-11 2009-06-11 Chartered Semiconductor Manufacturing, Ltd. Method of forming high-k dielectric stop layer for contact hole opening
US8354347B2 (en) * 2007-12-11 2013-01-15 Globalfoundries Singapore Pte. Ltd. Method of forming high-k dielectric stop layer for contact hole opening
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US7001838B2 (en) 2006-02-21
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US6887796B2 (en) 2005-05-03
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JP2004528716A (en) 2004-09-16
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US20040121600A1 (en) 2004-06-24

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