LOW DAMAGE PHOTORESIST STRIP METHOD FOR LOW-K DIELECTRICS
Improved methods for stripping photoresist and removing etch-related residues from dielectric materials are provided. In one aspect of the invention, methods involve removing material from a dielectric layer using a hydrogen-based etch process employing a weak oxidizing agent and fluorine-containing compound. Substrate temperature is maintained at a level of about 160° C. or less, e.g., less than about 90° C.
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This application is a continuation of and claims priority to U.S. application Ser. No. 12/636,601, titled “LOW DAMAGE PHOTORESIST STRIP METHOD FOR LOW-K DIELECTRICS,” filed Dec. 11, 2009, and a continuation-in-part of and claims priority to U.S. application Ser. No. 13/462,660, titled HIGH DOSE IMPLANTATION STRIP (HDIS) IN H2 BASE CHEMISTRY,” filed May 2, 2012, which is a divisional of and claims priority to application Ser. No. 12/251,305, titled “HIGH DOSE IMPLANTATION STRIP (HDIS) IN H2 BASE CHEMISTRY,” filed Oct. 14, 2008 (issued as U.S. Pat. No. 8,193,096), all of which are incorporated herein in their entireties for all purposes.
BACKGROUNDThe present invention pertains to methods for stripping photo-resist material and removing etch-related residues from the surface of a partially fabricated integrated circuit in preparation for further processing.
Damascene processing techniques are often preferred methods in many modern integrated circuit manufacturing schemes because it requires fewer processing steps and offers a higher yield than other methods. Damascene processing involves forming metal conductors on integrated circuits by forming inlaid metal lines in trenches and vias in a dielectric layer (inter-metal dielectric). As part of the Damascene process, a layer of photoresist is deposited on a dielectric layer. The photoresist is a light-sensitive organic polymer which can be “spun on” in liquid form and dries to a solid thin film. The photosensitive photoresist is then patterned using light through the mask and wet solvent. A plasma etching process (dry etch) is then used to etch exposed portions of dielectric and transfer the pattern into the dielectric, forming vias and trenches in the dielectric layer.
Once the dielectric layer is etched, the photoresist must be stripped and any etch-related residues must be thoroughly removed before subsequent processing to avoid embedding impurities in the device. Conventional processes for stripping photoresist employ a plasma formed from a mixture of gases with the presence of oxygen in the plasma. The highly reactive oxygen based plasma reacts with and oxidizes the organic photoresist to form volatile components that are carried away from the wafer surface.
Highly oxidizing conditions are also generally unsuitable for use on low dielectric constant (low-k) materials. Low-k materials have been used as inter-metal and/or inter-layer dielectrics between conductive interconnects in many modern devices to reduce the delay in signal propagation due to capacitive effects. The lower the dielectric constant of the dielectric material, the lower the capacitance of the dielectric and the lower the RC delay of the integrated circuit. Typically, low-k dielectrics are silicon-oxide based materials with some amount of incorporated carbon, commonly referred to as carbon doped oxide (CDO). It is believed, although not necessarily proven, that the oxygen scavenges or removes carbon from the low-k materials. In many of these materials such as CDOs, the presence of carbon is instrumental in providing a low dielectric constant. Hence, to the extent that the oxygen removes carbon from these materials, it effectively increases the dielectric constant. As processes used to fabricate integrated circuits moves toward smaller and smaller dimensions and requires the use of dielectric materials having lower and lower dielectric constants, it has been found that the conventional strip plasma conditions are not suitable.
What are needed therefore is improved and more efficient methods for stripping photoresist and etch-related materials from dielectric materials, especially from low-k dielectric materials.
SUMMARY OF THE INVENTIONThe present invention addresses the aforementioned need by providing improved methods for stripping photoresist and removing etch-related residues. In one aspect of the invention, methods involve removing material using a hydrogen-based etch process employing a weak oxidizing agent and fluorine-containing compound. Substrate temperature is maintained at a level of about 160° C. or less, e.g., less than about 90° C.
In certain embodiment, the methods involve introducing gas comprising a weak oxidizing agent, fluorine-containing compound and hydrogen into the reaction chamber, and applying RF power to form a plasma within the reaction chamber to convert at least a portion of the material to gaseous form, thereby removing at least a portion of the material from a partially fabricated integrated circuit. As stated previously, methods may be used to remove photoresist and/or residues from the etch process. Methods may be effectively implemented on Damascene devices, including single and dual Damascene devices.
According to various embodiments, the weak oxidizing agent comprises at least one of carbon dioxide, carbon monoxide, nitrous oxide, nitric oxide and nitrogen dioxide and water. In a particular embodiment, the weak oxidizing agent comprises carbon dioxide. In certain embodiments, the gas comprises between about 0.1% to about 10.0% carbon dioxide by volume. In some embodiments, the gas further comprises at least one inert carrier gas such as helium, argon or nitrogen. In certain embodiments, the gas does not comprise molecular oxygen.
According to various embodiments, the fluorine-containing compound comprises at least one of nitrogen trifluoride (NF3), sulfur hexafluoride (SF6), hexafluoroethane (C2F6), tetrafluoromethane (CF4), trifluoromethane (CHF3), difluoromethane (CH2F2), octofluoropropane (C3F8), octofluorocyclobutane (C4F8), octofluoro[1-]butane (C4F8), octofluoro[2-]butane (C4F8), octofluoroisobutylene (C4F8), fluorine (F2), and the like. In a particular embodiment, the weak oxidizing agent comprises nitrogen trifluoride. In certain embodiments, the gas comprises between about 5 ppm to about 10% nitrogen trifluoride by volume.
Methods of the invention may be implemented on any size wafer. Most modern wafer fabrication facilities use either 200 mm or 300 mm wafers. Process conditions may vary depending upon the wafer size. If a 300 mm wafer is used, the total flow rate of gas may range between about 1,000 sccm and about 40,000 sccm. If carbon dioxide is used as the weak oxidizing agent, the flow rate of carbon dioxide may range between about 10 sccm and about 2000 sccm, e.g., 800 sccm. If nitrogen trifluoride is used as the fluorine-containing gas, the flow rate of nitrogen trifluoride may range between about 1 and 20 sccm, e.g., 5 sccm. Typically, the RF plasma power for a 300 mm wafer ranges between about 300 Watts to about 3 Kilowatts for a plasma. Methods may be implemented using a direct or remote plasma.
During the application of plasmas to the work piece surface, substrate temperatures can range between about 50° C. degrees and about 160° C. In certain embodiments, work piece temperatures are maintained at about 90° C. or less. Example chamber pressures can range between about 300 mTorr and about 2 Torr. In some embodiments, the wafer is held at a bias.
As mentioned previously, methods of the invention may be used with low-k dielectric materials, including carbon-doped low-k dielectric materials such as carbon-doped oxides (CDOs). Methods of the invention can be implemented on both non-porous and porous dielectric materials, including CDOs and other compositions.
Methods of the invention may be implemented in any suitable reaction chamber. The reaction chamber may be one chamber of a multi-chambered apparatus or it may be part of a single chamber apparatus. In some embodiments, a multi-stage removal process is used, with the fluoride-containing compound used only a subset of the stages. In certain embodiments, the fluoride-containing compound is used only in a first set of stages, e.g., a first stage. In embodiments wherein a multi-station apparatus is used, the fluoride-containing compound may be used as part of process gas used to generate a plasma in the first station, for example.
These and other features and advantages of the present invention will be described in more detail below with reference to the associated drawings.
In the following detailed description of the present invention, numerous specific embodiments are set forth in order to provide a thorough understanding of the invention. However, as will be apparent to those skilled in the art, the present invention may be practiced without these specific details or by using alternate elements or processes. In other instances well-known processes, procedures and components have not been described in detail so as not to unnecessarily obscure aspects of the present invention.
In this application, the terms “semiconductor wafer”, “wafer” and “partially fabricated integrated circuit” will be used interchangeably. One skilled in the art would understand that the term “partially fabricated integrated circuit” can refer to a silicon wafer during any of many stages of integrated circuit fabrication thereon. The following detailed description assumes the invention is implemented on a wafer. However, the invention is not so limited. The work piece may be of various shapes, sizes, and materials. In addition to semiconductor wafers, other work pieces that may take advantage of this invention include various articles such as printed circuit boards and the like.
As mentioned previously, methods of the invention may be used to efficiently and effectively to remove photoresist and etch-related materials from a low-k dielectric materials. Methods of the invention are not limited to low-k dielectrics. Methods are also not limited to any particular category of low-k dielectrics. For instance, described methods may be effectively used on dielectrics with k values less than 4.0, dielectrics with k values less than about 2.8 and dielectrics with k values less than about 2.0 (“ultra-low-k” or ULK dielectrics). The low-k dielectric may be porous or non-porous (sometimes referred to as a “dense” low-k dielectric). Generally, low-k dense dielectrics are those having k values no greater than 2.8 and low-k porous dielectrics are those having k values no greater than 2.2. Low-k dielectrics of any suitable composition may be used, including silicon oxide based dielectrics doped with fluorine and/or carbon. Non-silicon oxide based dielectrics, such as polymeric materials, may also be used. Any suitable process may be used to deposit the low-k dielectric, including as spin-on deposit and CVD deposit techniques. In the case of forming porous dielectrics, any suitable method may be used. A typical method involves co-depositing a silicon-based backbone and an organic porogen and subsequently removing the porogen component, leaving a porous dielectric film. Other methods include sol-gel techniques. Specific examples of suitable low-k films are carbon based spin-on type films such as SILK™ and CVD deposited porous films such as Coral™.
Methods of the invention use plasmas that are produced from gases that contain hydrogen and a weak oxidizing agent, and in certain processing operations, a fluorine-containing compound. One skilled in the art will recognize that the actual species present in the plasma may be a mixture of different ions and molecules derived from the hydrogen, weak oxidizing agent and/or fluorine-containing compound. It is noted that other species may be present in the reaction chamber, such as small hydrocarbons, carbon dioxide, water vapor and other volatile components as the plasma reacts with and breaks down the organic photoresist and other residues. One of skill in the art will also recognize that reference to the initial gas/gases introduced into the plasma is/are different from other gas/gases that may exist after the plasma is formed.
ProcessReferring to
Referring to
As shown in
Referring back to
This operation is typically performed in a different reaction chamber from the chamber where the etch took place. Such a reaction chamber may be referred to as a stand-alone “strip unit.” Any apparatus with a suitable plasma reaction chamber can be used. The system may provide a direct (in situ plasma) or remote plasma.
It should be noted that the operation 103 may be used in certain embodiments to replace a conventional oxygen-based strip that is performed in the same reaction chamber in which the etch took place and typically involves exposure to an oxygen-based plasma. This oxidizing partial strip operation can damage some low-k dielectric materials, and may not be performed in certain implementations. Thus in certain embodiments, the wafer is provided in operation 101 without having previously undergone such a strip process in the etch chamber.
Referring again to
The total flow rate of gas, the relative amount of weak oxidizing agent and fluorine-containing compound and other conditions in the strip chamber can vary depending upon, among other factors, plasma type (downstream versus direct), RF power, chamber pressure, substrate (wafer) size and type of weak oxidizing agent used. In some examples using the Novellus Gamma™ system (downstream plasma system), the plasma may comprise between about 0.1% to 10% carbon dioxide by volume and between about 5 ppm to 10% nitrogen trifluoride (if present) by volume.
In addition to hydrogen, weak oxidizing agent, and fluorine-containing gas, a carrier gas such as helium, argon or nitrogen may be used. The carrier gas is typically an unreactive gas. For shipment and handling safety reasons, commercial hydrogen is available in mixtures with noble gases such as helium. These commercially available gas mixtures may be used for the methods of this invention.
After the majority of the photoresist and etch residue has been removed during plasma strip in operation 105, one or more additional plasma strip or wet clean operations may be performed. It should also be noted that in multi-station apparatuses, operations 103 and 105 may each be performed over one or more than one station.
The wafer is typically temperature controlled during exposure to the plasma. In particular, the temperature such that it is no more than about 200° C., no more than about 160° C., no more than about 150° C., no more than about 140° C., no more than about 130° C., no more than about 120° C., no more than about 110° C., no more than about 100° C., no more than about 90° C., no more than about 80° C., or no more than about 60° C. In particular embodiments, the substrate is maintained at temperature no more than about 90° C. It has been found that these relatively low temperatures are critical in certain embodiments to preventing significant damage to the ULK film.
Higher temperatures allow a faster etch rate; however, it has been found that more fluorine is required to etch as the temperature is increased. As a result, damage to the dielectric is increased. Damage can also occur, however, by long exposure times that come from using low temperatures. However, it has been found that temperatures in the ranges described above can prevent or reduce damage within the constraints of these competing effects.
In one example, the following process conditions were used to produce a low damage strip:
Station 1: 20 slpm H2/0.8 slpm CO2/5 sccm NF3
Station 2-5: 20 slpm H2/0.8 slpm CO2
Stations 1-5: 0.9 Torr/90° C./3.5 kW RF plasma/103 seconds per station
In certain embodiments, the temperature is raised for one or more operations after exposure to the fluorine-containing plasma. For example, a temperature of less than 160° C. or less than 90° C. may be used during exposure to the fluorine-based plasma, and raised prior to or during exposure to the one or more operations that use fluorine-free plasmas. Temperature may be raised in stages in certain embodiments, with later stations using higher temperatures than earlier ones. The higher temperature may be within the range described, or may be higher than that described. For example, in certain embodiments, later stations can use higher temperatures such as 285° C. However, in many embodiments, temperature is maintained at a low temperature throughout the strip process.
The above description provides examples of removing photoresist using low temperature hydrogen-based plasmas, in particular processes that involve exposing photoresist and etch-related residues to a plasma generated from hydrogen gas, wherein the wafer temperature is maintained at a low temperature, e.g., less than about 200° C., less than about 160° C., less than about 150° C., less than about 140° C., less than about 130° C., less than about 120° C., less than about 110° C., less than about 100° C., less than about 90° C., less than about 80° C., or less than about 60° C. In certain embodiments, the gas used to generate the plasma consists essentially of hydrogen gas in one or more operations. In alternate embodiments, one or more of a weak oxidizing agent, a fluorine-containing gas and a carrier gas may be added to the hydrogen gas in one or more operations, as described above. Examples of process gas chemistries that may be employed to generate a plasma for the low-temperature exposure operations include H2; H2/CO2; H2/CO2/NF3 and H2/NF3, with other weak oxidizing agents and fluorine-containing agents described above substituted for or added to CO2 and NF3, respectively. Depending on the characteristics of the photoresist and etch residue present, these may be used at any or all of the removal operations depicted in
For example, to remove the “skin,” the gas used to generate the hydrogen-based plasma may have essentially no CO2 or other weak oxidizing agent present. Also, in certain embodiments, there may essentially no NF3 or other fluorine-containing gas present. The gas used to generate the hydrogen-based plasma to remove the bulk photoresist may have essentially no CO2 or other weak oxidizing agent present. In many embodiments, there may essentially no NF3 or other fluorine-containing gas present, as described above. However, NF3 or other fluorine-containing gas may be present in certain embodiments.
ApparatusAs mentioned, any suitable plasma reaction chamber apparatus may be used. Suitable plasma chambers and systems include the Gamma 2100, 2130 I2CP (Interlaced Inductively Coupled Plasma), G400, and GxT offered by Novellus Systems, Inc. of San Jose, Calif. Other systems include the Fusion line from Axcelis Technologies Inc. of Rockville, Md., TERA21 from PSK Tech Inc. in Korea, and the Aspen from Mattson Technology Inc. in Fremont, Calif. Additionally, various strip chambers may be configured onto cluster tools. For example, a strip chamber may be added to a Centura cluster tool available from Applied Materials of Santa Clara, Calif.
As mentioned, in some embodiments, the apparatus of the invention is a strip unit dedicated to stripping photoresist from wafers. Generally, such a strip unit tool will have multiple wafer process stations so that multiple wafers may be processes simultaneously.
During typical manufacturing mode, wafers are processed in batch mode. Batch mode processing can increase wafer though-put and is therefore commonly used in manufacturing operation. In batch mode, each wafer is transferred to, and processed in, each of stations 431, 433, 435, 437, 439 and 441. For example, a typical batch mode process will proceed as follows: A wafer is first loaded into load station 431 where it is preheated with a heat lamp. Next, robotic arm 443 transfers the wafer to strip station 433 where it is plasma processed using a fluorine-based plasma for a time period sufficient to strip off about ⅕ of the photoresist. Robotic arm 443 then transfers the wafer to strip station 435 where it is plasma processed using a non-fluorine process for a time period sufficient to strip off about another ⅕ of the remaining photoresist. This sequence is continued such that the wafer is processed at strip stations 437, 439 and 441. At strip station 441, the photoresist should be largely removed and the wafer is then unloaded from the strip unit tool.
Although various details have been omitted for clarity's sake, various design alternatives may be implemented. Therefore, the present examples are to be considered as illustrative and not restrictive, and the invention is not to be limited to the details given herein, but may be modified within the scope of the appended claims.
Claims
1. A method of removing material from a work piece after an etch process, the method comprising:
- forming a first plasma from a gas comprising hydrogen and a fluorine-containing compound;
- exposing the work piece to the first plasma;
- forming a second plasma from a gas comprising hydrogen; and
- exposing the work piece to the second plasma,
- wherein the work piece temperature is maintained at a temperature below about 200° C. during exposure to the first plasma, wherein at least some of the material is removed from the dielectric layer by exposure to the first and second plasmas and the removed material comprises one or more of photoresist and residue from the etch process.
2. The method of claim 1, wherein the material comprises photoresist including a bulk portion and a skin covering the bulk portion.
3. The method of claim 2, wherein exposure to the first plasma removes the skin.
4. The method of claim 1, wherein the gas from which the first plasma is formed further comprises an oxidizing agent selected from carbon dioxide, carbon monoxide, nitrous oxide, nitric oxide and nitrogen dioxide and water.
5. The method of claim 1, wherein the fluorine-containing compound is comprises at least one of nitrogen trifluoride (NF3), sulfur hexafluoride (SF6), hexafluoroethane (C2F6), tetrafluoromethane (CF4), trifluoromethane (CHF3), difluoromethane (CH2F2), octofluoropropane (C3F8), octofluorocyclobutane (C4F8), octofluoro[1-]butane (C4F8), octofluoro[2-]butane (C4F8), octofluoroisobutylene (C4F8), and fluorine (F2).
6. The method of claim 1, wherein the second plasma is generated from a fluorine-free process gas chemistry.
7. The method of claim 1, wherein the work piece temperature is maintained at a temperature below about 160° C. during exposure to the first plasma.
8. The method of claim 1, wherein the work piece temperature is maintained at a temperature below about 120° C. during exposure to the first plasma.
9. The method of claim 1, wherein the work piece temperature is raised to a second temperature during exposure to the second plasma, the second temperature greater than the workpiece temperature during exposure to the first plasma.
10. The method of claim 9, wherein the second temperature is no more than about 285° C.
11. The method of claim 1, wherein the same workpiece temperature is maintained during exposure to the first and second plasmas.
12. The method of claim 1 wherein the work piece has not undergone a previous oxygen-based plasma photoresist stripping operation.
13. The method of claim 1, wherein the material is removed from a dielectric layer.
14. The method of claim 1, wherein the material is removed from an oxide.
15. The method of claim 1, wherein the material is removed from a carbon-doped oxide.
16. A method of removing material from a dielectric layer on a work piece as part of a partially fabricated integrated circuit after an etch process, the method comprising:
- forming a first plasma from a gas comprising hydrogen, a fluorine-containing compound, and an oxidizing agent selected from carbon dioxide, carbon monoxide, nitrous oxide, nitric oxide and nitrogen dioxide and water;
- exposing the work piece to the first plasma to thereby remove one or more of etch-related residue and photoresist from the dielectric layer, wherein the work piece temperature is maintained at a temperature below about 200° C. during the exposure to the first plasma.
17. The method of claim 16, wherein the work piece temperature is maintained at a temperature below about 120° C. during the exposure to the first plasma.
18. The method of claim 16, wherein the volume percentage of the oxidizing agent is between about 0.1% and 10% in the gas and the volume percentage of the fluorine-containing compound in the gas is no more than 10%.
19. The method of claim 16, wherein the volume percentage of the fluorine-containing compound in the gas is no more than 1%.
20. An apparatus for removing material from a work piece surface comprising:
- a reaction chamber comprising: a plasma source, a showerhead positioned downstream of the plasma source, and a work piece support downstream of the showerhead, said work piece support comprising a pedestal and temperature-controlling mechanism to control a temperature of a work piece supported on the work piece support; and
- a controller for executing a set of instructions, said set of instruction comprising instructions for forming a first plasma from a gas comprising hydrogen, a weak oxidizing agent and a fluorine-containing compound; exposing the work piece to the first plasma; forming a second plasma from a gas comprising hydrogen and a weak oxidizing agent; exposing the work piece to the second plasma, and maintaining the work piece at a temperature below about 200° C. during the exposure operations.
Type: Application
Filed: Oct 29, 2013
Publication Date: May 1, 2014
Applicant: Novellus Systems, Inc. (Fremont, CA)
Inventors: David Cheung (Foster City, CA), Ted Li (Sunnyvale, CA), Anirban Guha (Milpitas, CA), Kirk Ostrowski (San Jose, CA)
Application Number: 14/066,587
International Classification: H01L 21/3105 (20060101);