TW201220006A - Plasma mediated ashing processes - Google Patents

Abstract

A plasma ashing process for removing photoresist, polymers and/or residues from a substrate comprises placing the substrate including the photoresist, polymers and/or residues into a reaction chamber; generating a plasma from a gas mixture comprising oxygen gas (O2) and/or an oxygen containing gas; suppressing and/or reducing fast diffusing species in the plasma; and exposing the substrate to the plasma to selectively remove the photoresist, polymers and/or residues from the substrate, wherein the plasma is substantially free from fast diffusing species.

Description

201220006 VI. Description of invention: [Reciprocal reference of relevant application] This case is the US non-provisional application filed on July 27, 2010, and the direct application case No. 12/844,193 and November 7, 2008] The application for the US Park is not a temporary application for patent application No. 12/275 394, ° electricity, the current part of the application for the continuation of the application and claims the rights and interests based on the two previous cases; in. BACKGROUND OF THE INVENTION The present disclosure relates generally to a plasma intermediate ashing process that effectively removes organic materials from a semiconductor substrate while being capable of reducing oxidation and/or erosion of the substrate during processing; and particularly with respect to plasma intermediate ashing methods, The plasma is substantially free of rapidly diffusing species. The integrated circuit process can generally be divided into the front end of the production line (fr〇nt end 〇f line ' FEOL) processing and the back end of the production line (back en(i 〇fUne, be〇l) processing. The FEOL process is focused on manufacturing the integrated circuit. Different components, while the BEOL process generally focuses on the metal interaction between the different components that form the integrated circuit. Reviewing the 涿縻芋 邀 邀 邀 ( (Inten^ti〇nal

Technology Roadmap for Semiconductors (ITRS) related to FEOL processing reveals important performance challenges for future components in many key areas, including plasma ashing. For example, the development of plasma ashing predicts that the target leakage of the 45 nm (nm) generation is no greater than 0.4 A for each cleaning step, while the 32 nm generation is no greater than 〇.3A. 201220006 Stones are smashing, sensitive substrate materials (such as implanted with extremely shallow dopants k; | electrical, metal gates and the like) are exposed to the photoresist during the process of removing photoresist It may be damaged during the removal process. The substrate phase, which may be caused by substrate intrusion such as (4), splashing, and the like: the portion of the substrate that is removed by the body, such as a missing substrate, the oxidation of the substrate, the change of the bleaching/potency of the change, or a combination thereof. form. These changes are undesired because they will change the enthalpy, chemical, physical properties of the substrate. In addition, if there is a small deviation in the distribution profile of the pattern formed in the lower layer, it may adversely affect the component performance, output, and reliability of the final integrated circuit. For example, in source and drain implant applications, a photoresist layer is formed on the source and drain regions of the germanium substrate prior to performing high dose implants. During the implantation process in high doses, the photoresist is subjected to relatively high energy ions whose cross-linking reaction depth caused by the photoresist t is almost equal to or slightly larger than the ion range. This parental reaction and the resulting hydrogen loss result in a hardened photoresist layer, which is commonly referred to as the shell layer. The physical and chemical properties of the shell vary depending on the conditions of the planting. It is generally more resistant to the plasma application ashing process than the underlying non-crosslinked photoresist. Because of this, more aggressive plasma chemicals are needed to remove the resist. At the same time, however, very shallow joint depths require extremely high selectivity during the removal of the agent. Leakage or deuterium oxidation from the source/drain regions must be avoided during high-dose ion implantation stripping. For example, excessive leakage can detrimentally alter the current saturation at a given applied voltage and cause parasitic leakage due to reduced joint depth, which detrimentally alters the electrical function of the component. Current plasma intermediate ashing methods are generally not suitable for this application. 201220006 Standup = Intermediary stripping process is typically based on oxygen (four), guide::! Cleaning steps. However, the oxygen-based process can vaporize the surface of the substrate, typically at about ιοΑ or greater. The plasma oxidation rate of 2:: or (4) is determined by the diffusion rate of the oxidized species. Since the thickness of the expander is proportional, the growth of the oxide thickness is directly proportional to the oxidization fan, and the square root of the growing window is proportional. Those skilled in the art can characterize the exposure time of electropolymerization. "The equation R is called parabolic growth, and its X2 + AX = B(t) line ι ΐΓ oxide thickness 't = time 'B = parabolic rate constant And A/B = linear rate constant. Surface oxidation AI is known to be controlled by the plasma resist stripping process. Therefore, many people think that the use of oxygen-based (IV)-based electro-accumulation is dry: no, 32% required for advanced logic components The latter and the more advanced latter require nearly "zero" substrate leakage and lead to new materials that are sensitive to the surface (eg embedded SiGe source/nopole, high k: very dielectric 'metal gate and NiSi contact for tradition ^, because the parabolic rate constant can be as high as (10) per second, so significant oxide growth can occur in exposure / only a few seconds. Similarly, has::: pass: two contain the electricity gathering process in addition to people Unacceptable substrate loss Ή leads to dopant bleaching. Other plasma ashing methods = also chemical chemistry f 'for example gas formation (N2 / H2); on the substrate oxidation a ' it provides good results' but because Low resist removal rate 201220006 has problems with yield. In addition, gas-based electropolymerization has often found changes in dopant distribution that adversely affect the electrical properties of the component. Because of this, the previous electricity Destructive intermediary ashing method It is considered unsuitable for the removal of photoresist from the advanced design specifications. Because of the inevitable problems caused by the ashing of the electropolymerization under the design rules of the material, such as substrate loss, dopant bleaching and Similarly, so many, the Lord has been directed to fish-type chemical removal of the photoresist. As will be demonstrated here, Application 1 has found a viable plasma-mediated stripping of spears suitable for advanced design rules: Provides minimal substrate loss, minimal dopant bleaching, and the like. It is important to note that the ashing process is significantly different from the etching process. Although both processes can be plasma-mediated, the etching process is clearly different from selective electro-convergence. The chemical removes part of the substrate surface through the opening through the photoresist mask to permanently transfer the image into the substrate. The etched package typically exposes the substrate to high energy at low temperatures and low pressures (millimeters). Desalination removes the selected portion of the substrate by physical removal. In addition, the selected portion of the substrate exposed to ions is generally removed at a rate greater than the removal rate of the photoresist mask. Generally refers to the photoresist mask and any polymer or residue formed during the removal of the button. The ashing plasma chemistry is far less aggressive than the etched chemistry and is generally chosen to remove the photoresist. The rate of lifting the layer is much greater than the rate at which the underlying substrate is removed. In addition, most of the ashing process heats the substrate to further increase plasma reactivity and wafer yield, and at relatively high pressures (the level of the bracket) Therefore, the residual and ashing process removes photoresist and polymeric materials for very different purposes, so completely different plasma chemistries and methods are required. Successful ashing methods are not used to permanently transfer images to substrates in 201220006. The successful ashing method instead consists of the removal rate of photoresist, polymer and/or residue without affecting or removing the underlying layer (4) substrate, oxide and nitride spacers, low-k dielectric materials and the like) Defined. Based on the foregoing, what is needed in this art is a workable solution to remove the photoresist required by advanced design rules, particularly with regard to removing photoresist after high dose ion implantation. [Invention] In one embodiment, a plasma ashing method for removing photoresist, polymer, and/or residue from a substrate includes: placing a substrate including a photoresist, a polymer, and/or a residue into a reaction a chamber; generating a plasma from a gas mixture comprising oxygen (〇2) and/or an oxygen-containing gas; suppressing and/or reducing rapidly diffusing species in electrical destruction; and exposing the substrate to a plasma for selective selectivity from the substrate The photoresist, polymer and/or residue are removed, wherein the plasma is substantially free of rapidly diffusing species. In another embodiment, a method of ashing an organic substance from a substrate includes: generating a plasma from a gas mixture comprising ruthenium or an oxygen-containing gas, and combining the plasma with atomic oxygen to sweep the gas; The substrate of the substance is exposed to the plasma and the organic material is selectively removed from the substrate. In yet another embodiment, a plasma apparatus for ashing photoresist, polymer, and/or residue from a substrate includes: a plasma generating member for generating a plasma, wherein the plasma is constructed substantially free of rapid A diffusing species, and formed by a gas mixture of an oxygen-containing gas and an atomic oxygen sweeping gas; and a processing chamber fluidly coupled to the plasma generating member, the processing chamber housing the substrate. 8 201220006 In yet another embodiment, an electro-convergence device for ashing photoresist, polymer, and/or residue from a substrate includes: an electro-distribution generating member for generating electro-convergence, (〇2) or a mixture of gases containing oxygen gas, and combined with atomic oxygen to sweep the gas; a sweeping material located between the plasma and the substrate, which is constructed to inhibit and/or reduce rapid diffusion in the electrical heel a species; and a processing chamber that covers the substrate and is in fluid communication with the plasma generating member to the 'violation chamber is configured to expose the substrate to a plasma that has suppressed and/or reduced rapidly diffusing species' to selectively The photoresist, the composition and/or the residue are removed. These and other features and advantages of the specific aspects of the present invention will be more fully understood from the following detailed description of the invention. It is defined by the narratives and not by the specific discussion of the features and advantages listed in the description of the invention. [Embodiment] We have identified the parabolic rate constant B for different oxidative species. As shown in Figure 19. The parabolic rate constants of oxygen ions and atomic species are orders of magnitude higher than the parabolic rate constants of molecular species (eg, (10) or 〇2*). Due to this discovery, the oxidation of ruthenium can be Two possible mechanisms are dramatically reduced: (1) replacing rapidly diffusing species such as 0+, 0_, or 〇* with a substantially slower diffusing molecular species; (7) nitriding surface oxides to 'reduce species diffusion through The rate of oxides in growth. Disclosed herein is a plasma intercalation ash 201220006 method for selectively removing photoresist, ion implantation photoresist, polymer, residue, and/or the like from a substrate. Apparatus. As will be described herein, among many advantages, the electro-disruption intermediate ashing method and apparatus provide, in particular, a relatively high ashing rate, minimal or no substrate loss, minimal or no damage to the underlying material (eg, High-k dielectric material), minimal or no dopant distribution change. As a result, the plasma-intermediate photoresist ashing method and apparatus described herein are suitable for 32-minute FEOL processing and exceed the base. Leakage must be kept to a minimum (1) at 1.0A) and the electrical properties need to be substantially unaltered by the photoresist removal process. In a specific aspect, the plasma intermediate ashing process generally involves the inclusion of oxygen (〇2). Or a gas mixture of oxygen-containing gases to produce a plasma, wherein the electricity is substantially free of rapidly diffusing species. Most of the atomic species produced by the plasma for ashing have high diffusion constants. It has been found to have a high diffusion constant. Atomic species can cause high levels of deuterium oxidation, which is an unwanted effect of the plasma ashing process. In other words, the plasma oxidation rate is controlled by rapidly spreading species. Therefore, 'fast diffusion species' as used herein (fast The term diffusing speeies generally refers to an atomic species having a high diffusion constant, i.e., a high parabolic growth rate constant of greater than about 0.0003 Α2 (Α2 / sec) per second. In a body-like 'rapidly diffusing species' at 270. (The parabolic rate constant is equal to or greater than about 0.02 A2/S. Exemplary rapid diffusion species that can be produced during normal plasma processing include, without limitation, reactive oxygen species (〇*), atomic oxygen (〇), ionic oxygen (〇 +, 〇·) and the like. As used herein, the terms "active nitrogen", "active oxygen" (active 0Xygen) and other similar active species (eg active hydrogen) generally refer to energy. The atom or molecule that is excited, but the species that is electrically neutral. 10 201220006 It is disclosed herein that the plasma intermediate ashing method of 7F is controlled by oxygen diffusion: thereby during plasma generation or during exposure to The subtraction of the substrate to be treated y can oxidize the parabolic rate constant of the rapidly diffusing species of the substrate: the measured diffusion rate, or the elimination and/or suppression of rapidly diffusing species in the plasma. To achieve this, the source of the plasma is Whether it is generated by microwave or radio frequency energy, it is optimized for the production of molecular species, in which the proportion of slowly diffusing molecular species to rapidly diffusing atomic species is reduced to a minimum of 2 The effect of the person's or the diffusion of the fast diffuser is reduced; 5 or both. In particular, the effect of the fast diffuser can be achieved by making the ratio of 02* or N0* to active oxygen (0*) Maximum and lower. Because the presence of active oxygen (which is the natural: product of oxygen or oxygen-containing gas plasma) is the mechanism of oxidation', reducing the active oxygen is effective in reducing the oxidation of the stone to two degrees. The diffusion rate of the diffuser can be reduced by nitriding the oxide. More specifically, the proportion of the active nitrogen emulsion (〇*) can be maximized to reduce the diffusion constant. "j and ° in a specific aspect" Plasma Intermediary Ashing Method - General Package: The ratio of reactive nitrogen to reactive oxygen species in the plasma is such that the ratio is 1 and can be paid from the plasma pair of oxygen (〇2) and nitrogen (N2) gas mixtures. Proportion of Reactive Oxygen Species. Figure 1 μ demonstrates the difference in the ratio of available reactive nitrogen and reactive oxygen species formed by electrolysis with nitrogen (10) gas: a comparison of the ratios available in the practice of the Applicant's invention. Shown in the 'previous skill' by oxygen and gas mixture It exhibits a ratio of reactive nitrogen to active oxygen that includes a relatively high amount of active hydrazine relative to the active gas; it has been found that this has nothing to do with the specific oxygen and nitrogen composition used to form the electrical polymerization of 201220006. Applicants have discovered a variety of mechanisms to increase the ratio of reactive nitrogen to reactive oxygen in the plasma, which is substantially greater than the ratio of plasma available from a gas mixture containing free oxygen and nitrogen.

------- g / small butyl milk loose. Referring to Figure 2', it is graphically shown that the oxide of the prior art is grown as a function of the oxygen (〇2) content of the gas mixture comprising both oxygen (〇2) and nitrogen (Nz) gases to form a plasma. The gas mixture evaluated included a mixture containing oxygen and nitrogen and a mixture comprising oxygen and forming gas, wherein the forming gas contained 3% hydrogen in nitrogen. As shown, even the impact of a trace amount of oxygen causes oxidation of the substrate, and the effect is reduced. The smallest "non-zero" surface modification is observed in 〇% of oxygen. With regard to the two gas mixtures, the oxidation rate of the car's high enthalpy is observed in the plasma formed by the formation of the gas, which indicates that it is formed in a specific state, and the plasma intervenes the ashing method to produce a reactive species. Including activity

It generally consists of mixing reactive gases from nitrogen and reactive oxygen species, and treating the specific components of the plasma gas mixture generally 12 201220006 as a specific specificity for changing the active web, and the ratio of VlL &+ nitrogen to active oxygen. Depending on the situation. ::5' plasma may be produced by gaseous nitrous oxide itself, or by a mixture of oxidized dinitrogen gas and _, oxidizing gas, inert gas, retort body and various combinations thereof. "A nitrogen gas or a gas-gas strip, a human At- emulsified nitrogen gas compound may further comprise a variety of additives' to increase the rate of photoresist removal and / or to make the material underneath (such as electricity) Damage to materials, substrates, metals, dopant concentrations, and the like is minimized. It should be noted that although the above specific reference to nitrous oxide is suitable as appropriate for use with oxygen (〇2) and nitrogen (N2) gases To increase the ratio of reactive nitrogen to active oxygen in the plasma, but it is also conceivable to include oxygen and other gases containing oxygen. Furthermore, the compound can be formed by two or more kinds of electropolymerization, which are treated by J. Cavity-to-card combination. For example, a plasma formed of an oxygen-containing gas may be mixed to cause electrical destruction by a nitrogen-containing gas. In this manner, one of the "can be formed by oxygen (02), and the other Plasma can be supplied by increasing the amount of reactive nitrogen The formation of a nitrogen-containing gas. In contrast, one of the plasmas may be formed of nitrogen (N2), and the other may be formed of an oxygen-containing gas. In yet another embodiment, an active hydrogen species is added or present ( H*) combined with reactive nitrogen (N*) and optional reactive oxygen species (〇*) species may be advantageous for certain applications, such as certain post-plant applications (especially with respect to residues) Removal of material) and certain high K/metal gate structures that can affect the performance of the element by metal oxidation. Provides low plasma by providing a controlled mixture of reactive nitrogen, active hydrogen species, and optional reactive oxygen species. Substrate damage (such as Si oxidation and / or Si loss) and low metal substrate oxidation (such as TiN, 13 201220006

TaN and/or W metal) while effectively removing photoresist and residue in relatively high yields. In some specific aspects, electropolymerization is formed by a gas composed of NH3. In other embodiments, the plasma is formed from a gas mixture of package #3, wherein Μ% constitutes a major portion of the gas mixture. For example, some specific aspects of the gas mixture may include greater than 5% by weight of NH3, and in other specific aspects, greater than 75%, and in addition other specific aspects are greater than 85%. For most ashing applications, gas compounds that have a preferred embodiment of the gas mixture of greater than or equal to 90% include, but are not limited to, nh3 and forming gases, Nh3 and n2, cis 3, and forming gases and oxygen. The presence of oxygen increases the rate of ashing, and by controlling the amount of oxygen present in the gas mixture, the process is provided with minimal leakage. As will be discussed in detail herein, various mechanisms for reducing rapidly diffusing species (eg, atomic oxygen species) in electrical destruction include the use of filters, sweeping gases, sweeping materials, money, and the like to excite Q2 and The rapidly diffusing species produced in the electrical destruction are removed and/or absorbed prior to exposure to the photoresist, thereby reducing the amount of rapidly diffusing species in the electropolymer. In addition, these gas-gathering materials produce a state-of-the-art molecular oxygen that is effective in terms of filaments without oxidizing the base material. Alternatively, the source of electrical destruction and the gas compound may be selected such that the proportion of slowly diffusing oxidant (eg, molecular oxidant) to the rapidly expanding oxidant (eg, atomic or ionic oxygen) is maximized, which may be: Any thought of any enhancements or self-contained. In doing so, the electric h includes the active hydrogen species. The enthalpy has been found to have a more aggressive ashing behavior for the ion implant blocking layer and has the least 201220006 sniper "such as substrate oxidation. The more aggressive ashing behavior of substrate invaders and similar ones can be used to efficiently ash photoresist materials that are typically considered to be difficult to ash, such as exposure to high energy dose ion implants. 〇se — implantation strip, drawing 8) Residues and similarities formed after shell etching of the photoresist. Figure 3 illustrates an exemplary apparatus for generating multiple plasma streams, generally indicated by reference numeral 10. The slurry apparatus 10 generally includes a gas transfer member 12, a plasma generating member 14, a processing chamber 16, and a discharge tube 18. The gas transfer member 12 includes a gas purifier (not shown) that is in fluid communication with one or more gases. Source 20, the latter being in fluid communication with the plasma generating member. Using microwave excitation as an example of a suitable energy source for generating plasma from a gas mixture, the plasma generating member 34 includes a microwave enclosure 36, which is generally divided into The cut rectangular box has a plasma tube 38 therethrough. As is known in the art, the microwave electropolymer generating member is constructed to excite the input gas into a plasma to produce a reactive species. The plasma generating member 304 may also be operated with a combination of RF energy excitation source, RF and microwave energy, or the like. The plasma tube 38 includes a plurality of gas inlets 22 (two of which are shown) 'from the gas transfer member 12 The gas 20 is thus fed into the portion of the plasma tube extending from the gas inlet and is connected downstream of the plasma energy source. In this manner, different plasmas are produced in the apparatus which are then mixed prior to exposure to the substrate. Once excited, the active species are introduced into the interior region of the processing chamber 16 to evenly transfer the reactive species to the surface of the workpiece 24 (e.g., the semiconductor wafer of the resist). In this regard, one or more baffles 26 28 is included in 15 201220006 processing chamber 16. Although the specific operation of the baffle is not described in detail below, additional information on such operations can be found in the transfer. U.S. Patent Application Serial No. 10/249,964, the disclosure of which is incorporated herein by reference in its entirety the entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire all all all all all all all all all all all all all all all all all all all all all all all all all all all all all all all all all all all all all all all all all all all all all all all all all all all all all all all all all all all all all all all all all all all all all all all all all all all all all all all all all all all all all all all all all all all all all all all It may be heated by an array of heating elements, such as a tungsten halogen lamp or a resistive heated chuck, which is not shown in the circle. The inlet 34 of the discharge tube 18 is in fluid communication with the opening of the bottom plate to receive the exhaust gas into the discharge tube 8 . Again, it should be understood that the plasma ashing apparatus 1 〇 represents an example of a device that may be used in conjunction with the practice of the present invention to produce different plasmas from subsequent mixing of different gas streams before the substrate is exposed to the plasma. The plasma equipment consists of a medium pressure plasma 'MPP system' operating at approximately 1 Torr to provide a lower electronic temperature, as well as a single plasma tube configuration and no baffle Slurry source (eg broad source area plasma) can be applied to different specific nitrogen-containing bodies including, but not limited to, N2, N20, NO, N2〇3 NH3, NF3, N2F4, C2N2, HCN, NOCM, C1CN, (CH3) 2NH, (CH3) NH2, (CH3) 3N, C2H5NH2, mixtures thereof and the like. Inert gases suitable for addition to the gas mixture include, without limitation, helium, hydrogen, nitrogen, helium, gas, helium, and the like. Suitable fluorine-containing gases which have active fluorine include those which are fluorine-reactive species upon excitation by a plasma. In a specific aspect, the fluorine gaseous compound is a gas under plasma formation conditions and is selected from the general formula. 16 201220006 • Group of CxHyFz compounds 'its + x is an integer from 0 to 4, Υ is an integer from 0 to 9' Ζ is an integer from 1 to 9, with the condition that χ = 〇 Both equal Bu and when y is 〇 ... to...: or a combination of such compounds. Alternatively, the gas containing gas may be f2, sf6 and mixtures thereof, if desired, including the fluorine-containing gas as defined by the above general formula CxHyFz. When exposed to the plasma, the fluorine-containing gas is less than about 5% of the volume of the electric monoxide gas mixture to maximize selectivity. In other specific aspects, when exposed to the plasma, the compound containing less than 3% of the total volume of the electropolymerized gas mixture is in other specific aspects, and when exposed to the plasma, it is fluorinated. The amount is less than about 1% of the total volume of the plasma gas mixture. Suitable reducing gases include, but are not limited to, gas-containing gases such as hydrazine, CH4, 3, CxHy (where χ is an integer from t to 4, 乂 is an integer from [to 8), and combinations thereof. The hydrogen-containing compound used produces sufficient atomic hydrogen species to increase the removal selectivity of the polymer and button residue formed during the characterization. A particularly preferred hydrogen-containing compound is present in the gaseous state and releases hydrogen under conditions of formation to form atomic hydrogen species such as free radicals or wind ions. The hydrocarbon-based hydrogen-containing compound gas may be partially substituted by a function (e.g., filling, gas or gas) or by oxygen, nitrogen, a trans- and an amine group. The helium hydrogen (H2) is preferably in the form of a gas mixture. In a specific aspect, the helium gas mixture is a gas containing hydrogen and an inert gas. A suitable inert gas example. Including argon, nitrogen, helium, neon and the like. A particularly preferred hydrogen mixture is the so-called forming gas (f_inggas, FG) which consists essentially of nitrogen and nitrogen. It is particularly preferred to form a gas' wherein the amount of hydrogen is from about 1 M% to about 5% by volume of the total formed gas composition of 17 201220006. Although an amount greater than 5% by volume can be utilized, safety is a problem due to the risk of hydrogen explosion. Suitable oxidizing gases include, but are not limited to, 〇2, 〇3, C〇, ch, H2〇, N2〇, N〇2, and the like. When an oxidizing gas is used, I prefer to remove any 〇* and 〇* species from the plasma prior to exposure to the substrate. As noted above, the factor that has been found to oxidize the substrate is that the substrate reacts with the 0 〇 and/or 0_ species. These species can easily diffuse through the growing Si〇x surface oxide, thereby resulting in a relatively thick oxide growth. The rapid diffusion of these two species can be accelerated by the electric field in which the surface oxide is present or reduced. Because of this, the strategy of minimizing the growth of oxides should solve several arguments, and also π: suppress the original? Or the formation of ionic oxygen (or the formation of any other rapidly diffusing species), reducing the rate of diffusion of the remaining fast diffusers and reducing or eliminating electric field and oxide charging. As noted above, the removal can be accomplished by increasing the pressure in the reaction chamber during the plasma treatment, changing the power density, adding the additive, adding a gas containing both nitrogen and oxygen (such as nitric oxide), using filtration. Implemented by devices such as atomic and ion filters. The plasma intermediate ashing process can be implemented in a conventional plasma ashing system. The invention is not intended to be limited to any particular plasma ashing hardware. For example. Alternatively, a plasma asher in which an inductively coupled plasma reactor is employed, or a downstream plasma asher, such as microwave driven, RF driven, and the like, may be used. In view of the present disclosure, the setting and optimization of a particular plasma asher will be familiar to those skilled in the art. Plasma ashers typically include electropolymerization 201220006 generation chambers and plasma reaction chambers. By way of example only, in a downstream microwave plasma asher of a 3 mm RpS320 available from Axcelis Technologies, Inc. (applicant), the substrate is heated in the reaction chamber to a temperature between room temperature and 45 ° C. . The temperature used during processing may be fixed or alternatively may be graded or stepped during processing. Increasing the temperature is a method used by those skilled in the art to increase the rate of ashing. The pressure in the reaction chamber is preferably reduced to about 〇. Torr or higher. More preferably, the pressure system operates in the range of from 0.5 Torr to about 4 Torr. For some applications (such as unwanted oxygen species (such as 0*, 〇-) to do the gas phase recombination system, so as to increase the ratio of reactive nitrogen to active oxygen in the plasma), can use more than 4 Torr Higher operating pressures, while some specific aspects use more than 1 Torr. The power used to excite gases and form a source of plasma energy is typically between about 1000 watts (W) and about 10,000 watts. For certain gas mixtures, the power is greater than 5000 watts to less than about 1 watt. For example, when the gas mixture includes NH3 as a main component (greater than 5〇%), it has been found that increasing the power to more than 5000 watts and less than 1 watt can be used to increase the active hydroquinone formed in the plasma, The rate of ashing can be advantageously increased. Furthermore, increasing the enthalpy of the active hydrogen species reduces metal oxidation. In some embodiments, the plasma is exposed to a gassing agent such that the amount of active hydrogen is reduced when desired. The power setting can also be adjusted to control the ratio of reactive nitrogen to active oxygen in the plasma, which can be applied to other types of plasma ashing tools. The power density of the plasma source (i.e., the power per gas volume) can also be adjusted to increase the amount of neutral and excited molecular species (e.g., and the like). In a specific aspect, the plasma can be produced at a power density of at least about 75 watts per 19,200,200,6,200,000 cubic meters per cubic centimeter; especially at least about 10 watts per cubic centimeter. The centimeters are at least XI (9) watts, :: special 疋. 疋 at least about 2 每 per cubic centimeter 〖, most specifically at least 300 watts in the mother cubic centimeter. Included 3, oxygen or oxygen and nitrogen (in a certain The gas mixture containing the nitrogen gas is fed into the chamber through the gas inlet. The gas is then exposed to a source of energy in the plasma generating chamber, such as microwave energy, preferably at about 1000 watts. And between about 1 〇 watt to generate excited or energetic atoms from the gas mixture. The resulting electropolymer comprises electrically neutral and charged particles and excited gas species, which are used in the gas I gas mixture. The gas is formed. In a specific aspect, the charged particles are selectively removed before the electrical device reaches the wafer. For a 3GG mm downstream electric ash, the total gas flow rate is preferably from about every minute. 500 to 12 inches 〇〇 standard cubic centimeters... (10) as eubic centimetei per minute, sccm) It has been found that the total gas flow rate can affect the emission spectrum of certain gas mixtures. For example, a lower total gas flow rate may be preferred for inclusion. NH3 is used as the main component of the gas mixture to increase the amount of active hydrogen in the plasma and increase the concentration of active molecular species. In one specific aspect, the total gas flow rate of the NH3 containing gas or gas mixture is less than 5 standards per minute. Standar (1 nter per minute 'Slm). In other specific cases, less than 4 sim; and in other specific aspects, less than 3.5 Slm. Photoresist, ion implantation photoresist, polymer, residue or A similar organic substance is selectively removed from the substrate by reaction with an atom that is excited or energized by the plasma (ie, 20 201220006 active species). The reaction can be optically detected to detect the endpoint, such as It is known to those skilled in the art. Alternatively, the plasma ashing process is followed by a rinsing step 'to remove volatile characters and/or wash away a removable compound formed during the plasma treatment. In one embodiment, although the rinsing step employs deionized water, it may also include ammonium hydroxide, sulfuric acid, hydrofluoric acid, or the like. The rinsing step (if used) It can include a spin rinse for about 1 to 10 minutes, followed by a spin drying process. For example, the plasma hardware configuration can be modified to increase the ratio of slow-diffusing species to rapidly diffusing species or increase the ratio of reactive nitrogen to reactive oxygen species. In one embodiment, a sweeping material (eg, an atomic and/or ionic oxygen interposer) and/or a catalyst material is disposed between the substrate and the plasma source such that an excited state of molecular oxygen is produced and the plasma is reduced. The amount of rapidly spreading species in the medium. This filter may be a catalytic filter material, a surface recombination transition, a gas phase recombination filter or the like. For example, the filter can be a surface reactive metal or metallic alloy, ceramic, quartz or sapphire material, while the reactive gas passes through the filter prior to interaction with the wafer surface. The efficacy of this filter can be enhanced by controlling the temperature of the reactive surface and the shape and surface roughness of the reactive surface. The location of the sweeping material can be in close proximity to the substrate because the excited state molecules have a relatively long lifetime. More specifically, the sweeping material can be located about 8 cm or less from the workpiece (substrate). In another embodiment, the plasma ashing tool using a double baffle is modified such that the upper baffle is formed of quartz (as opposed to sapphire), and it is also found in 2012 20126 that the addition of reactive nitrogen to reactive oxygen species has been found. proportion. A similar effect was observed when sapphire or other materials were used instead of quartz to form a plasma tube. A suitable sweeping material that can be used to reduce the content of rapidly diffusing species (specifically 〇, 〇*, 〇+ and/or 〇-) in the plasma, with a recombination coefficient equal to or greater than about 5x10·4 〇 Although exemplary materials for sweeping atomic oxygen are listed in the table of FIG. 2A, they may include, without limitation, metals (eg, B, Mg, A Be, Ti, Cr, Fe, Μη, Νί, Rb, Ir, Pb, Sr, Ba, Cs, alloys thereof, intermetallic compounds (for example, PrNi5, NtNi) and the like), ceramics (for example)

Ti02, Ta205, Zr〇2, a12〇3, FeO, and the like), semiconductor (for example

Si, Ge and the like) or organometallic. Exemplary atomic oxygen sweep gases include, but are not limited to, legs 3, C0, N0, CH4, other carbonitrides, carbon compounds, and the like. Catalysts suitable for forming an active gas include, without limitation, metals (e.g., Fe, Co, Ni, Ru, Re, pt, M?, pd, and the like) or Tao Jing (e.g., MgAl2?4 and the like). The formation of reactive nitrogen can also be promoted by the use of gas additives (eg He, Ar, Kr, Xe), elemental design of electropolymer sources (eg, beam-derived surface materials and temperatures), operation of electropolymer sources Methods (eg, excitation frequency, power density, electron temperature, gas mixing ratio) or the like. 2 Another specific aspect of the sweeping material is directly or indirectly heated to a temperature of 2 〇〇〇 c or higher to enhance the re-combination of the tablets. Figure 17 graphically shows that the recombination of ai2〇3 and S1〇2 is a function of temperature. The rate of recombination of most materials increases at elevated temperatures. In addition, the other body shape can be used to replace the material with ω· ΛΓ using % degassing gas or add 2012 201220006 to sweeping materials and/or gas gathering materials. The atomic oxygen sweep gas may be combined with the above-described plasma source, wherein the sweep gas is effective in further reducing the atomic germanium content to about 1/4 or less. An exemplary sweep gas used to further reduce rapidly diffusing species is NH3, where the ratio of the 3 to 〇2 in the gas mixture will exceed 2 to 1. In another aspect, the downstream plasma ashing device is utilized to selectively remove charged particles prior to exposure of the reactive species to the substrate, such as commercially available from Axcelis Technologies, Inc. of Beverly, MA, under the trademark RpS32. The downstream microwave oven talks about the ashes. For FEOL treatment, it is desirable to remove substantially all of the charged particles from the reactive species before exposing the substrate to reactive species. In this manner, the substrate is not exposed to charged particles that may adversely affect the electrical properties of the substrate. The substrate is exposed to an electrically neutral reactive species for removal of photoresist, polymer and/or residue, which is exposed to nitrogen (10), oxygen (〇*), optional hydrogen (9), and the like. Active species. The additional/emergence requirement of advanced design rules is the need to maintain the compatibility of the electropolymerization method with high-k dielectric and intermetallic materials. To promote compatibility, the oxidized dioxane mixture or any of the various mechanisms discussed above for the ratio of active nitrogen to active oxygen can be included, selected to reduce damage to these materials while maintaining adequate response. Sex to remove photoresist and implanted shells> White Cup I layer. Suitable chemical additives include, but are not limited to, materials containing _, such as CF4, CHF3,

Br, HCl, Cl2, BCl3, CH3C1, CH2ci2 and the like. r. The dentate-containing additive discussed above can be effectively used to enhance the migration of the portion of the photoresist layer called the ion-implanted photoresist layer. In other specific aspects, a plasma comprising reactive nitrogen, active oxygen, active hydrogen species can be used to effectively remove the shell. For example, the plasma can be formed from a gas mixture of Nh3, 〇2, which forms a gas which effectively removes the underlayer and the underlying photoresist. In other embodiments, a multi-step plasma ashing process can be used to remove the shell layer, followed by an aggressive plasma chemistry, followed by a less aggressive plasma chemistry, to remove the underlying The non-crosslinked photoresist, polymer, residue, which is optionally followed by a passivation or residue removal plasma step. For example, to protect the gate and/or gate dielectric during plasma ashing of the ion implant photoresist, the first step may alternatively include a nitrous oxide gas mixture comprising a dentate-containing additive. Forming plasma to remove light

A plasma of a ratio of nitrogen to active oxygen.

For 矽 there is a ashing selectivity greater than 10,000: 10,000:1. 24 201220006 Sub-detection concrete, this method is a multi-step process, which effectively removes the separation and resistance. As noted above, the ion implantation photoresist generally includes a lower density of the upper part of the upper 而# lower than the lower part and a function of exposure to the ion 2 implant. The multi-step process can be packaged (IV) - step: exposing the photoresist layer The substantially entire upper portion is removed from a low density plasma of less than about 70 watts per cubic centimeter formed by a gas mixture comprising bribes 3, wherein NH3 constitutes a major portion of the gas mixture. Money can be made the same. Plasma to remove the lower part. For example, the photoresist layer can be removed by exposure to a high density plasma of at least about 7 watts per cubic centimeter formed by a gas mixture comprising NH3. NH wherein NH3 constitutes the main part of the gas mixture. Any residue that may remain may then be removed using a different plasma without NH3, such as a plasma formed from a gas mixture of nitrogen or gas. The surface can also be passivated if desired. The photoresist is generally an organic photosensitive film, and the substrate for transferring the image to the bottom can be applied to ashing for use in g-line, i-line, DUV, 193 nm, 157 nm, electron beam, Euv, and the like. Immersion lithography applications or similar photoresists. These include, but are not limited to, novolacs, polyvinyl phenols, acrylates, aldehydes, polyamidones, ketones, cyclic olefins or the like. Those skilled in the art will be aware of other photoresist formulations suitable for use in the present invention in view of this disclosure. The photoresist can be positive or negative depending on the selected photoresist chemical and developer. The substrate can be essentially any semiconductor substrate used to fabricate integrated circuits. Suitable semiconductor substrates generally include or may comprise germanium, strained germanium, germanium substrates (such as SiGe), germanium on insulators, high-k dielectric materials, gold 25 201220006 genus (eg, /, Ti, TM, TaN, and the like) ), GaAs, carbide, nitride, oxide and the like. Advantageously, the method is applicable to an element having material lost from the semiconductor substrate (e.g., over a mismatched area). It is not intended to limit the scope of the invention below for illustrative purposes only. EXAMPLE 1 In this example, the photoresist on the ruthenium substrate was exposed to nitrous oxide flaking chemicals in a RapidStrip 32 〇 plasma ashing tool commercially available from Axcelis Technologies. The photoresist is a tantalum photoresist and has a thickness of 99 μm deposited on the ruthenium substrate. The plasma chemistry is a nitrous oxide gas flowing at a pressure of 7 standard liters per minute (sim) to a pressure tTorr temperature of 240°. C. The power is set to a 350 watt plasma ashing tool. The ashing rate, cross-wafer uniformity, and oxide growth of the nitrous oxide plasma stripping process are compared to oxygen-free reducing plasma (forming gas) and oxygen-based plasma. The reducing plasma was formed by a gas mixture forming a gas (3% hydrogen in nitrogen) at a flow rate of 7 slm into a plasma ashing tool having a pressure of 1 Torr, a temperature of 240 ° C, and a power setting of 3,500 watts. The oxygen-based plasma uses 90% oxygen (〇2) and 1% of the formation gas (3% hydrogen in the nitrogen) to flow to a temperature of 240 at 7 slm. 〇, the power is set to 3500 watts of electric ashing tools. The ashing rate and non-uniformity were measured after the photoresist was exposed to individual plasma for 8 or 15 seconds. Oxide growth was measured by exposing the unexposed Shishi substrate to individual electric beams for 300 seconds. 26 201220006

Figure 4 shows the results. As expected, A-Bippen's oxide-based plasma oxide growth is significantly about 12 A, and the exhibition specification 八# &, n respects the mother 77 4, the highest ashing rate of about 7.8 microns. While t, the reducing electricity and the nitrous oxide plasma showed a significant improvement over the oxygen-based plasma, but with a lower ashing rate. The electropolymerization phase based on nitrous oxide shows less oxide growth than the reducing plasma; compared to about 4 people of the reducing plasma, it is in ^, ^ ^ ^ ^ J Λ 一The plasma of nitrous oxide is about 3.0 Torr. Obviously, the nitrous oxide-based plasma exhibits an ashing rate of about 4.4 microns per minute compared to a ashing rate of about 1 〇 micrometer per minute of the reducing plasma. Meanwhile, under the same processing conditions The ashing non-uniformity of the nitrous oxide-based plasma (non-uniformity = 2.8%) is significantly better than the oxygen/forming gas (> 10%). Example 2 In this example, a small amount of CF4 was added to a different plasma gas mixture and processed in a RapidStrip S320 plasma ashing tool. The Shixi substrate is exposed to different plasma chemicals and the growth of oxides is measured. The results are shown in Table 1 below. In each case, a variety of plasmas were formed using a gas composition with a flow rate of 7 s 1 in for a plasma ashing tool with a pressure of 1 Torr and a power setting of 3,500 watts. Table 1 Plasma Chemical Process Time (seconds) Oxide Growth cf4/ n2o 103 3.24 CF4/ 3% 〇2 / Forming Gas 103 9.54 CF4 / 90% 〇2 / Forming Gas 103 8.76 3% 〇2 / Forming Gas 140 9.82 27 201220006 As shown, the addition of a small amount of CF4 during the formation of plasma results in minimal substrate loss, as evidenced by the growth of oxides, and it is advantageously expected to produce more energetic species, as observed with respect to the example work. As a result, this should effectively increase the ashing rate. CF"N2〇 plasma has the highest ratio of reactive nitrogen to active oxygen, which also exhibits the least amount of oxidation. Example 3 In this example, in terms of shatter loss, oxide growth, and oxide loss, a RapidStrip 32 〇 plasma ashing tool and a plasma formed of nitrous oxide (also labeled as new technology) were used. The substrate damage was measured as compared to the prior art 〇2/forming gas mixture with plasma having no small amount of tetrafluorinated. The composition of the forming gas is 3 in the nitrogen. Hydrogen. The results are graphically shown in Figure 5A. In each case, a variety of plasmas were formed using a gas mixture having a flow rate of 7 slm into a pressure iTorr, a temperature of 24 Torr, and a plasma ashing tool with a power setting of 3,500 watts. Substrate damage includes (1) 矽 矽 矽 绝缘 绝缘 绝缘 绝缘 绝缘 绝缘 绝缘 绝缘 绝缘 绝缘 绝缘 绝缘 绝缘 绝缘 ii ii ii ii ii ii ii ii ii ii ii ii ii ii ii ii ii ii ii ii ii ii ii ii ii ii ii ii ii ii ii ii ii ii ii ii ii ii The ruthenium oxide is lost. Figures 5B and 5c compare scanning electron microscopy images after ρ-MOS high dose ion implantation cleaning applications. The SEM image shows plasma stripping followed by deionized water rinsing, where the plasma is formed from a mixture of 〇2 and A/H2 gases (Fig. 5C) and is formed by nitrous oxide gas, which indicates the essence. The residue removal capability of the plasma from the nitrous oxide gas mixture is improved. The results clearly show that the plasma having a relatively high ratio of active nitrogen to active oxygen substantially reduces substrate damage. The residue was observed from an oxidative plasma without carbon tetrafluoride 28 201220006. In addition, as shown in the figure. As noted in Figures 5B and 5C, the use of a chemical-nitrogen plasma significantly improves the removal of the residue. Example 4 For example, during the electropolymerization process, dopant leakage, substrate loss, and ashing rate were monitored, and the various plasmas used were composed of -oxidized-nitrogen gas, forming gas (3% Η2, 97α/&amp ; 匕匕 emulsified a nitrogen 俨 m. /, w 幻 2 (6), oxygen (9 〇%) and gas forming κ have two gas volume forming gas (that is, 9 〇% & and 1〇%, - All of the electropolymerization is formed by a total gas generator of 7 Slm and a microwave power of 3,500 watts. The substrate is charged with ',,, to 240 during the plasma treatment. The oxidation of Shixi is still from the eight/emulsification process time of 5 minutes.

The process time for removal is 8 seconds ^ ^ A 疋 shirt times 15 seconds. For the measurement of dopant profile, the carpet-type Shixi wafer is implanted with As or BP" crystal 0 and then exposed to various ashing plasmas for 5 minutes, and annealed at (9) generation for 1 sec. . Secondary ion mass spectrometry (seeQndary-cafe "speet_, SIMS" analysis was performed to determine the contour of the doping Gonglongxin knife cloth, and sheet resistance (RS) was measured to determine the sheet resistance. The results are graphically shown in Figure 6. If you do not use the highest active nitrogen to the ratio of active oxygen, the 'electricity' exhibits robust behavior for both AS and BF2 implants, as well as higher 2 ashing rates and lower oxidation rates. In addition, as expected The plasma formed by the gas mixture including oxygen exhibits an unacceptably high oxidation. Example 5 This example demonstrates the effect of an active gas-rich configuration compared to the configuration of a quartz tube. (Non-nitrogen-rich configuration), the construction of the RPS320 plasma source with a sapphire tube (configured with active nitrogen 29 201220006) does result in reduced ruthenium oxidation (Figure 7). Figure 8 shows this example rich The nitrogen configuration (sapphire plasma tube, compared to the quartz plasma tube) does cause an increase in reactive nitrogen, while the amount of active oxygen remains virtually unchanged, while the corresponding proportion of reactive nitrogen to active oxygen increases. demonstration Optimized configuration of nitrous oxide plasma, which includes optimized microwave power 'temperature' plasma tube composition, while showing substantially reduced ruthenium oxidation. As shown by 'relative to standard oxygen formation In the case of electrical destruction due to gas composition, all plasmas formed from nitrous oxide exhibit lower oxidation as a function of removal of the resist. In addition, lowering temperature and power settings results in lower oxidation and increase. The ashing rate. Furthermore, the plasma formed by nitrous oxide exhibits a much faster ashing rate than the gas-forming control plasma. Example 6 This example was analyzed using an optical emission spectrometer. The plasma formed by nitrous oxide is derived from the electropolymerization of each gas with respect to 90% oxygen and 10% of the formation gas (standard plasma process formed by 3〇/〇Η2 / 97% NO). The RpS320 was produced with 3,500 watts and a total gas flow rate of 7 slm. The optical emission of the plasma was collected by the optical emission spectrometer of 0cean Optics Inc. through the wafer height of the processing chamber. Figure 9 graphically demonstrates the wavelength of intensity. Function. worth It is intended to be a signal between about 300 and 380 nm, which corresponds to the n2* active species (produced by a plasma formed by nitrous oxide). In contrast, the standard electropolymerization process is at these wavelengths. No resolvable amount of n2* was observed. Thus, the ratio of active enthalpy to reactive nitrogen in the quasi-plasma process of 201220006 is significantly higher than that of nitric oxide-nitrogen. Although not limited by theory, it is believed that N2* It helps to reduce the oxidation of alpha in the nitrous oxide process (because the yttrium oxide interface has obvious nitridation 'as shown in Figure 21), but it also appears to cause a reduction in the ashing rate. In addition to this observation, the figure It also graphically shows that the nitrous oxide-based process produces significantly more NO. Embodiment 7 In this embodiment, an optical emission spectrometer is used to measure the ratio of reactive nitrogen species to reactive oxygen species as a function of microwave plasma, which is formed by nitrous oxide gas using RapidStrip 32 〇 plasma The ashing tool, the plasma chemistry, is formed by nitrating nitrous oxide gas at a pressure of 7 standard liters per minute (slm) into a pressure ίοTorr, a plasma ashing tool at a temperature of 24 〇〇c. As shown in Figure 10, the increase in ratio is a function of the reduction in microwave power, with a ratio of 1.2 observed at a minimum evaluation setting of 2.5 kW. The relative amount of ruthenium surface oxidation under nitrous oxide plasma conditions was also shown, which demonstrates that the amount of shi oxidized has a good correlation with the ratio of reactive nitrogen to reactive oxygen species in the plasma. Example 8 In this example, an optical emission spectrometer was used to measure the ratio of reactive nitrogen to reactive oxygen species, wherein the plasma was formed by (丨) nitrous oxide gas, (η) with CF4 additive. Nitrous oxide gas; (out) a mixture of 9 〇〇 / 〇 oxygen and 10% forming gas (3% h2 / 97% N2); and (lv) 90% oxygen and 1% nitrogen mixture. For demonstration purposes, the measured amounts of reactive oxygen and reactive nitrogen in the different plasmas shown in Figure 加以 are normalized to reflect the 〇2Ma (4) value. The ratio of the corresponding active gas to active oxygen is substantially higher than the electric I formed by the nitrous oxide gas mixture, and lower than the plasma formed by the 〇2+FG gas mixture, which is related to the amount of ruthenium oxide reported earlier. Have a good connection. It is worth noting that the amount of active oxygen is similar in all four evaluation plasmas, and the amount of reactive nitrogen in the plasma is significantly different. EXAMPLE 9 In this example, Figure 12 graphically illustrates the amount of ruthenium oxidation of an oxidative plasma as a function of electron temperature. The plasma formed by 90% oxygen and 1% by volume of the forming gas shows that the ruthenium oxidation is exponentially added as the electron temperature of the plasma increases. Low Zeolite oxidation needs to be maintained at a low electron temperature below about 5. 〇 electron volts. Example 10 In this example, the oxide growth of the tantalum substrate of various plasmas and the ashing rate of the photoresist were measured. The plasma was formed as a different gas mixture and using a RapidStrip 320 plasma asher with a power setting of 3500 watts, a gas flow rate of 7 Sim, and a temperature of 245 °C. The gas mixture includes: (a) 〇2 and forming gas (3% hydrogen/nitrogen); (b) n2〇; (c) n2O + 0.3% CF4; (d) bribes 3 and 02; (e) gas formation ( 3% hydrogen/nitrogen) + 10% N20; and (1) 1^-1^+1%% να. Prior to photoresist removal, the ruthenium substrate has the following four implants (!) amorphized implants; (ii) carbon implants; (iii) halogen implants; and (iv) extended implants +. A top-down scanning electron micrograph after the ion implantation, photoresist ashing, and wet cleaning steps, the cleaning step including a conventional ammonium hydroxide-over 32 201220006 hydrogen peroxide mixture (ammonium hydroxide-hydrogen peroxide mixture) , ΑΡΜ) / Sulfuric peroxide mixture (SPM). The APM cleaning step involves exposing the substrate to a NH4OH:H2〇2:H2〇 mixture (ammonium hydroxide-hydrogen peroxide mixture), also known as SCI (Standard clean 1, Standard Clean 1) or RCA 1. The SPM method, also known as "piranha clean," involves exposing the substrate to a ΗΑ〇4: Ηζ〇2 solution at 100 °C to 130 °C. The substrate is then rinsed with deionized water and dried. As shown, 'all micrographs are clearly residueed, with the exception of the substrate treated with a plasma formed by a mixture of (c) N2〇 + CF4 and (d) NH3 + 〇2. Bottom Table 2 below provides oxide growth and ashing rate dilution for various electropolymerizations. The results of the single oxide growth represent the oxide growth measured after a single treatment of the wafer with the corresponding electrochemistry of Table 2. Each wafer and electropolymerization chemistry are essentially the same, thereby showing different electrical t chemistries = efficacy. Twenty times the oxide growth rate represents the wafer to be electropolymerized: the oxide growth measured after 2 treatments. It is believed that the measurement of twenty gas growths substantially reduces measurement errors. Gasification Table 2

33 201220006 NH3 + 30% 〇9 A 0.83 ----* 2 0 NH3+10% FG 一----- 0 9 N^O ———· 0.54 ---------- 4 Π 〇2 / FG 1.15 1, ——--- 7 Q n2o+cf4 1.95 / . 〇.....----- 3.0 ----~~-___3.0 It can be seen from the 20-time oxide growth measurement The electrical breakdown formed from the N2〇+cF4 gas tail compound has a relatively high damage to the Asahi substrate (as compared to other 'plasma chemistries), as evidenced by the amount of oxide growth. In contrast, the electro-destruction formed by the gas mixture including NH3 + 〇 2 gas exhibited the least amount of Shixia oxidation (0.43 A / time, 1% 〇2 mixture), which is equivalent to the loss of 〇19 people. It is far below the 奈·3Α threshold of the 32nm generation set by ITRS. During the oxidation process, it is assumed that each enthalpy consumed during oxidation is converted to 2.2 Å of cerium oxide. Therefore, 〇43Α measured by oxide growth indicates that 0.19Α of yttrium is converted to yttrium oxide (〇19Α χ 2 2 people = 〇43Α) β change ratio / G ΝΗ3 + 30 /ό 〇2 gas mixture is provided) The rate of removal of the resist, but also increases the amount of damage to the sputum. The 9〇%NH3_F(} mixture has a lower ruthenium substrate oxidation than the 9〇% NH3 〇2 mixture, but also exhibits a lower ashing rate, which in turn reduces the yield. Example 11 In this example, Several types of electro-accumulating chemistries for high-dose implant stripping (HDIS) were evaluated for enthalpy loss, TiN oxidation, ashing rate, qualitative residue removal, and plant species dopant retention.矽 的 曰 - g · 疋 疋 石 石 石 石 石 石 石 石 石 石 石 石 石 石 石 石 石 石 石 石 石 石 石 石 石 石 石 石 石 石 石 石 石 石 石 石 石 石 石 石 石 石 石 石 石 石 石Different Thunder and Chemicals in the RapidStrip320 Plasma Ashing Tool. Thickness is measured before and after processing. For TiN gasification, every #^t 虱化汗, including TiN-coated substrates, is exposed to different electricity. The measurement of the slurry chemical β metal 惫tq beech is to compare the sheet resistance (Rs) before and after the plasma treatment. Qualitative measurement of residue removal. Perform secondary ion mass spectrometry (SIMS) analysis to determine the blending Distribution of debris in the temple of the wheel. Table 3

V application ashing chemicals

Si loss (A / time)

Key HDIS n2o 0.24

FG 0.20 90% NH3 and 〇2 70% NH3 and 〇2 丨.19 0.37 Metal oxidation TiN △ Rs (%) 47 -10 2 Ashing residual rate As-doping B-doping (micron impurity/dispensing Missing loss, clock) Except (%) (%) Excellent 4. Distinct -5.3 -3 -i〇0_ Poor -2 -7 Excellent - ii - Heterogeneous 2. 〇〇 - Different 35 201220006 90% NH3 and ~ 0.2 ~ 0 0.9 Excellent - FG S〇2 and FG 0.52 45 7.80 Good. 2.5 13 NH3 / 〇2 practices provide the lowest leakage [minimum metal (Ti) oxidation, excellent photoresist and residue removal properties Thereby providing effective electrokinetic chemicals for applications after high dose ion implantation. Example 12 In this example, an optical emission spectrometer was used to monitor the diverse active species of plasma produced by a gas mixture of 90% NH3 and 10% 02 at different power settings. The plasma was formed using a RapidStrip 320 plasma asher with a power setting of 4000 watts or 7800 watts, a total gas flow rate of 5 slm, a pressure of 1 Torr, a chuck temperature of 275 ° C, and a chamber wall temperature of 140 °C. Figure 13 graphical representation of OH* (at 309 nm), N2* (at 337 nm), H2* (at 486 nm), H* (at 656 nm), 〇2* (at 777 nm) The emission intensity set at different powers. As shown, 'increasing the power to more than 5 〇 0 〇 watts significantly increases the emission of active hydrogen (H* and Η/). In addition, an increase in activity was observed for active n2*. There is clearly no significant emission intensity associated with atomic oxygen (〇*) in the spectrum. Although some oxygen in the milk mixture apparently reacts with reactive nitrogen to form a living I. The information in the face clearly indicates that when using NR] gas and its mixture to generate electricity, the power setting can be used to adjust the amount of activity. 36 201220006 can be used to set the desired ashing rate. Example 13 In this example, the emission intensity of the various active species produced by the plasma of the NH3/1〇%〇2 gas mixture was monitored by an optical emission spectrometer as a function of total gas flow rate and pressure. The plasma is formed using an IntegraES plasma asherder with a power setting of 7 watts, a total gas flow rate of 3.5 slm or 7 slm, a pressure of 65.65, 1 〇, 1.5 or 2 Torr, and a chuck temperature of 275 °C. . Figure 14 graphical representation of OH* (at 309 nm), N2* (at 337 nm), Η 2* (at 486 nm), Η* (at 656 nm), Ο, (at 777 nm) The emission intensity set by different pressures and total gas flow rates. As shown, the pressure has minimal or no effect on the formation of diverse active species. However, active hydrogen (Hslt and Η,) exhibits a strong dependence on the total gas flow rate. Significantly comparable amounts of active hydrogen (Η* and η2*) relative to higher total gas flow rates are produced at lower total gas flow rates. In contrast, reactive nitrogen (Ν/) and active oxygen (〇*) did not exhibit a sensible response to pressure or flow rate. Example 14 In this example, the effect of controlling the oxygen diffusion process is exemplified. Figure 15 shows an optimized configuration of the plasma generated from Ν2〇 gas and an optimized configuration of the electric beam generated from the ΝΗ3 / 〇2 gas mixture, both of which include optimization at 27〇〇c Microwave power density (> 1 watt / cubic centimeter). The optical emission spectrum shown in Figure 16 shows how the added NH3 sweeping gas completely removes all measurable atomic oxygen. Both of these plasma configurations show a substantial reduction in helium oxidation; because in the case of NH3, the sweeping gas has been effectively removed = some atomic oxygen, while in the case of ΝΖ0, the sweeping gas has enhanced the molecular pair of 37 201220006 atoms The ratio provides effective nitridation of the surface oxide. In addition, the third group, L-Bell, demonstrates the largest oxide growth and the loss of the stone, which represents the standard ο] and the formation of gas plasma stripping, which has not been optimized to reduce the amount of rapidly diffusing species among them. - Nitrous oxide plasma and ammonia/oxygen plasma have substantially reduced the rate of parabolic growth such that the resulting ruthenium oxidation is only about a single layer. EXAMPLE 1 In this example, an optical emission spectrometer was used to analyze the plasma formed by ammonia and oxygen using the controlled oxygen diffusion method described herein, with respect to the formation of 9% oxygen and 10%. Standard plasma process formed by gas (3. /.H2 / 97% N2). The plasma from each gas was produced in RpS32. The optical emission spectrum of the plasma was collected by an optical optical spectrometer from Ocean Optics through a viewing height of the crystal height of the processing chamber. Figure 1 ό Graphical demonstration of wavelength as a function of intensity. Of note are the emission signals between about 300 and 400 nm (which correspond to the 〇Η* active species) and the emission signals between about 750 and 800 nm (which correspond to the 〇* active species). Both rapidly diffusing species are produced in a plasma formed by standard oxygen and gas forming processes. In contrast, the electrowinning formed by ΝΗ3 / 〇2 does not observe the achievable amount of 〇* at these wavelengths, thus indicating that the plasma does not have these rapidly diffusing species. At the same time, it is worth noting that there is a transmission signal between about 3 〇 400 and 400 nm (which corresponds to ο, active species). As noted above, it has been found that increasing the ratio of 〇2* to 0* reduces oxidation and loss. Thus, the ratio of molecular oxygen to atomic oxygen (〇2* : 〇*) is significantly higher than that in the standard plasma process. 'Example 16 38 201220006 In this example, the recombination coefficient of quartz and alumina is shown as a function of temperature in Figure 7. The graphical representation of the graph shows that the regrouping factor of Sui Huaming, a sweeper for rapidly diffusing atomic species, has increased compared to standard quartz materials. In general, as the temperature rises, most of the material undergoes an increase in atomic oxygen recombination. As can be seen in Figure 17, when the temperature 増 is added to 300. (: or higher, the recombination factor is increased by more than 5 times. In order to achieve a more efficient atomic recombination, the recombined surface should be heated directly or indirectly to a temperature of 300 ° C or higher. Example 1 7 kg For example, the concentration of Ο/ and 〇* in the plasma formed by ammonia and oxygen using the controlled oxygen diffusion method described herein is measured as a function of the power density of the plasma source. A power density exceeding 100 watts per cubic metric will effectively increase the concentration of 〇2*. Without being bound by theory and as described above, it is believed to increase the molecular species of the excited state (eg relative to atomic species (eg 0* or The proportion of 〇) will improve the overall ashing: 'including less bismuth oxidation. For example, &, optimize power density and match: controlled oxygen diffusion plasma formation and optional sweep gas or Materials 'some of these are effective in virtually eliminating rapidly diffusing species in plasma and reducing oxide growth and loss. The use of Qiaohui here is only to describe specific specific aspects, not to limit this hair As used herein, the singular forms "-" and "the" _ also include the plural unless the context clearly dictates the τ, and the use of @汇"第_", "第二", and the like is not implied. Any specific order is included to identify individual components. Further understanding of the word 39 201220006 "includes" and / or "includes" and / or "contains" when used in this statement, indicates that there are features, areas , integers, steps, operations, Yuan Mingshu ^ , T ^ j ^^ ^ ^ $ number, steps, operations, elements and/or components, but does not preclude the presence or addition of one or more other features, A region, an integer, a step, an operation, an element, a component, and/or a group thereof. Unless otherwise defined, all terms (including technical and scientific terms) used herein have the same meaning as the embodiment of the present invention. The same meaning that is commonly understood by the general practitioners. It will be understood that, for example, the commonly used words: the vocabulary defined by the dictionary should be interpreted as having the meaning associated with the related art and the second, and will not be ideal. Or an over-formal tolerance to interpret, unless explicitly defined as such. 2 has already referred to the embodiment of the present invention with reference to the specific embodiments: etc. Those skilled in the art will understand that it can be done a variety of variations. This I replaces its redundancy' without deviating from the specific state of the invention. It is suitable for 2 (four) many modifications to make the special condition or material have a hip-like shape without deviating from its The basic scope. Therefore, it is contemplated that U is not limited to the specific mode of performing the τq of the present invention, but is a package & mt β , body W, a specific aspect of the present invention. In contrast, the use of the first, flute _ * bamboo flavor in the scope of the specific aspect. This use of -, m ^, etc. 3 sink does not indicate any order or importance. Furthermore, the use of a distinction between a certain element and another element indicates that there is a limit to the indefinite article that does not indicate the quantity, but rather a reference item. 201220006 [Simplified Description of the Drawings] A detailed description of the above specific aspects of the present invention can be best understood by reading the drawings, which are exemplary embodiments, in which: Figure 1 shows a bar graph display The relative amount of reactive nitrogen produced by oxygen (〇2) and nitrogen (n2) compared to the reactive oxygen produced by the plasma formed according to the present invention, wherein the ratio of reactive nitrogen to active oxygen is substantial It is larger than the oxygen and nitrogen plasma available from the prior art. Figure 2 graphically demonstrates that normalized yttrium oxide grows as a function of the oxygen content of the gas mixture used to form the plasma, wherein the gas composition includes oxygen (〇2) and nitrogen (NO mixture and oxygen (〇2) and forming gas ( Η] / Μ?) Mixture. Figure 3 schematically illustrates an exemplary plasma apparatus constructed to enhance the ratio of reactive nitrogen to active oxygen, which is substantially greater than oxygen and nitrogen plasma available from prior art. Μ · Demonstration bar graph showing the prior art electro-destruction and formation of nitrous oxide-based plasma (N2〇) compared to a gas mixture of oxygen (〇2) and forming gas (N2 / Ηζ) The yttria growth and photoresist ashing rate of another prior art plasma formed by gas (7) 2/%). The bar graphs illustrated in Figures 5A-C show substrate damage based on nitrous oxide based on prior art oxygen-based (〇2)-based plasma, and after demonstration of ρ-MOS high-dose ion implantation cleaning applications. Scanning electron microscopy image. Loss, (8) the growth of the 7 oxide on the test wafer; and (4) the loss of the tantalum oxide from the Shixi thermal oxide test wafer, and the image-like demonstration of the electrical stripping and then rinse with deionized water. From the previous two figures of 201220006, FIG. 5B is about the plasma formed by the gas mixture of 〇2 and n2 / h2, and FIG. 5C is about the electric charge formed by the gas of oxidizing gas. Figure 6 shows a bar graph showing the nitrous oxide-based plasma, the gas-based plasma, the oxygen-based and gas-forming plasma, and the H2/N2 electro-destruction of the high-hydrogen content. The loss of debris and the rate of light ashing are a function of the plasma chemistry. Figure 7 graphically demonstrates the enthalpy oxidation of ruthenium oxide based electrolysis, oxygen, and gas forming plasma as a function of resist removal. This figure demonstrates nitrous oxide plasma conditions with and without active nitrogen configuration and optimized nitrous oxide stripping plasma conditions. Figure 8 is a graphical representation of the bar graph showing the phase of active oxygen and reactive nitrogen from the nitrous oxide electropolymerization without the active nitrogen configuration and the corresponding reactive oxygen and reactive nitrogen. proportion. Figure 9 is a graphical representation of the function of the wavelength of the electro-optic emission of nitrous oxide based on the electro-optic emission intensity of the electropolymer formed by oxygen and forming gas. - Figure 10 graphically demonstrates the relative amounts of reactive nitrogen and reactive oxygen in a nitrous oxide-based plasma at different power settings and the corresponding ratio of active gas to active oxygen. Also shown is the corresponding yttrium oxide growth under these plasmas. Figure 11 is a graphical representation of a nitrous oxide-based electricity t, a nitrous oxide-based plasma with a CF4 additive, a plasma formed by a ruthenium 2 gas and a gas, and a gas of 〇2 and N2. The relative amount of reactive nitrogen and active oxygen of the formed plasma and the corresponding ratio of active nitrogen to active oxygen. Figure 12 graphically illustrates the amount of ruthenium oxidation of an oxidative plasma as a function of electron temperature 42 201220006. Figure 2 is a graphical representation of the amount of microwave power at a different power setting for the power 4 generated from 9〇% of NH3 and 〇%. Figure 14 graphically illustrates the total gas flow rate and pressure as a function of optical emission intensity at a fixed power setting of plasma from 90% Li 3 and 1% 〇2. ‘The formation of a gas-like plasma, a plasma generated from ammonia and oxygen. Figure 15 graphically demonstrates the generation of plasma from oxygen and nitrous oxide gas, resulting in loss of self-loss and oxide growth as a function of time. Figure 16 is a graphical representation of the relative intensity of the optical emission spectrum of the electropolymer formed from the mixture of ammonia and oxygen gas compared to oxygen and forming gas (5% hydrogen in N2) as a function of wavelength. Figure 17 graphically demonstrates the recombination coefficient of quartz and bismuth oxide materials and temperature dependence. Figure 18. Graphical demonstration of the splitting of the knife as a function of plasma source power density over the normalized concentration of oxygen compared to the active atomic oxygen. Figure 19 graphically demonstrates the parabolic growth rate measured at 270oC for a diverse variety of oxygen species. Figure 20 is an atomic representation of several materials. Figure 2 shows a graphical representation of nitrogen and surface oxides. The gas is re-twisted and combined with the rate table. The components from Ν* to 0* high-ratio plasma are for the sake of brevity and clarity. Those skilled in the art will demonstrate in the schematic diagram, but not necessarily in proportion. 43 201220006 [Main component symbol description] None 44

Claims (1)

201220006 VII. Patent Application Range: 1. A plasma ashing method for removing photoresist, polymer and/or residue from a substrate, the method comprising: Substrate comprising a photoresist, a polymer and/or a residue into a reaction chamber; generating a plasma from a gas mixture comprising oxygen (〇2) and/or an oxygen-containing gas; inhibiting and/or reducing the plasma a rapidly diffusing species; and exposing the substrate to the plasma to selectively remove the photoresist, polymer and/or residue from the substrate, the plasma of which is substantially free of rapidly diffusing species. • The method of plasma ashing in Section 1 of the patent application, wherein the fast-diffusing species is at 270. . The parabolic rate constant is equal to or greater than about 0.02 A2/S. 3. The method of electrical ashing according to item i of the patent application, wherein the rapidly diffusing species comprises ^, ..., . - comprising a combination of at least one of the foregoing. [2] The method of claim 5, wherein the suppressing and seeding (4) t: rapidly diffusing species in the plasma comprises: contacting the fast diffusing species with a surface comprising a sweeping material. = The method of electric ashing in item 4 of the patent application, its scattered species. The material is further inhibited and/or reduced by the rapid expansion. 6. The method of electrification ashing according to claim 5, wherein the surface is heated at or above a temperature of about 200 ° C. 7. For the plasma ash person 1G method of claim 5, the recombination coefficient of the sweeping material is equal to or greater than 5 χΐ〇·4. ^ 8. The ashing method of claim 5, wherein the sweeping material comprises cerium oxide 'aluminum, aluminum oxide, nickel, nickel alloy, platinum, platinum alloy, titanium, oxidized chin, silver, silver alloy,嫣, 'Emulsified tungsten, tungsten alloy or a combination comprising at least one of the foregoing materials. 9. The plasma ashing method of claim i, wherein the atomic oxygen content is suppressed by adding a sweep gas. The plasma ashing method of claim 9 wherein the sweeping gas comprises NH3, CO, N〇戎CH, Atb~human^1NU or LxHy, wherein the sweeping gas constitutes a sufficient portion of the gas mixture to reduce atomic oxygen 11. The plasma ashing method of claim 10, wherein the gas mixture further comprises a gas forming mixture comprising hydrogen (h2) and nitrogen (N2). 12. The plasma ashing method of claim </ RTI> wherein the gas core comprises H N2 〇 纟 wherein the ratio of reactive nitrogen to active oxygen of the plasma is greater than that which can be obtained from any mixture of oxygen and nitrogen. Electric damage The ratio of the nitrogen to the active hydrazine. 13 The plasma ashing method according to claim 1, wherein the method comprises: changing the power density applied to the gas mixture. 14. The electricity as claimed in claim 13 A plasma ashing process, wherein the plasma generating step comprises excitation at a power density of at least about 75 watts per cubic centimeter.... 46 201220006. 15. A plasma ashing method according to the patent scope, wherein the electricity The pulp power is from a microwave or RF power source. 16. A method of ashing an organic material from a substrate, comprising: generating a plasma from a gas mixture comprising ruthenium or an oxygen-containing gas, wherein the plasma is substantially absent a rapidly diffusing species; combining the plasma with an atomic oxygen sweep gas; exposing the substrate having the organic material to the plasma; and selectively removing the organic material from the substrate. η· The method of claim 16, wherein the sweeping gas reduces the atomic oxygen content of the plasma to about 1/4 or less. 18. The method of claim 17, wherein the sweeping gas comprises NH3, CO, C〇2, CxHy (X is an integer from 1 to 4, y is an integer from i to 8) or includes, in combination with at least one of the foregoing, 19. The method of claim 18, wherein The volume ratio of the sweep gas to 〇2 is equal to or too much about 2 to 1. 20_-A plasma device for ashing photoresist, polymer and/or residue from a substrate, the device comprising: for generating a plasma a plasma generating member, wherein the plasma is formed of a gas mixture comprising oxygen (〇2) or an oxygen-containing gas, combined with an atomic oxygen sweep gas; a sweeping material positioned between the plasma and the substrate, Constructed to inhibit and/or reduce rapidly diffusing species in the plasma; and a processing chamber for covering the substrate and in fluid communication with the plasma generating member, the processing chamber being constructed to Exposure to plasma that has been inhibited and 201220006 = = = species to selectively τ σ and/or residue from the substrate. The special plasma equipment for the 20th item, including the dioxin, oxidized Ming, Lu, Zhen alloy U alloy, titanium, oxidized, #, silver, silver alloy, tungsten, oxidation Tungsten, a tungsten alloy or a combination comprising at least one of the foregoing. 22. The plasma apparatus of claim 2, further comprising a pyrolysis gas, which is produced by recombination of atomic oxygen. 23. The plasma apparatus of claim 22, wherein the excited molecular oxygen produced is transferred to the wafer in the half-life of the excited molecular oxygen. 24. The plasma of claim 22 The device in which the excited molecular oxygen produced is delivered to the wafer within 1 millisecond. 25. The plasma apparatus of claim 23, wherein the excited molecular oxygen produced is delivered to the wafer at a gas flow rate of more than 4 standard liters per minute. 26. The plasma apparatus of claim 23, wherein the sweeping material is configured to be about 6 cm or less from the substrate. 27. The plasma apparatus of claim 20, wherein the gas mixture is excited by microwave or RF energy at a power density of about 75 watts per cubic centimeter or more to form a plasma. 28. The plasma apparatus of claim 20, wherein the sweeping material is heated directly or indirectly to a temperature of 200 ° C or higher. 29. The plasma apparatus of claim 20, wherein the sweeping gas 48 201220006 • the body is NH3, NO, CO, a hydrocarbon gas or a combination comprising at least one of the foregoing. 3. A plasma apparatus as claimed in claim 20, wherein the sweeping material is constructed to reduce the active oxygen content of the plasma to about 1/2 or less. Eight, the pattern: (such as the next page) 49