TWI389219B - Method for forming dielectric or metallic films - Google Patents

Description

Method of forming a dielectric or metal film

It is an object of the present invention to provide a method and composition that meets the need to form a film that has excellent electrical quality and high conformality and that avoids the use of multiple forming steps to achieve uniform coverage and height. Conformal. Another object of the present invention is to provide a film which minimizes the chlorine and carbon content which both degrade the electrical properties of the film. Still another object of the present invention is to provide the ability to control the M/Si ratio in the film over a wide range without altering the precursor solution. Still another object of the present invention is to avoid the quality and conformality that occurs when a liquid precursor (including multiple components) solution is evaporated, or when a carrier gas is bubbled through a liquid helium source. problem.

Background of the invention

The semiconductor device is fabricated using a thin gate dielectric material (typically cerium oxide) between the underlying germanium substrate and the gate electrode. A layer of dielectric film is deposited on a substrate to form a gate dielectric material. Typical processes for the growth of dielectric films include oxidation, chemical vapor deposition, and atomic layer deposition methods. When the integrated circuit device is shrunk, the thickness of the gate dielectric material must also be scaled down. However, under the characteristics of compromised power, semiconductor manufacturers have reached the limit that the thickness of conventional gate dielectric materials can be reduced. To achieve the same dielectric properties, a thicker new material exhibiting a higher dielectric constant can be used instead of cerium oxide. This dielectric property is not degraded by using a cerium oxide dielectric material (only some of the thickness of the atomic layer). Therefore, a new composition or method is required to produce a dielectric film having a higher dielectric constant than that of yttrium oxide (referred to as a "high-k value dielectric material"). These "high-k dielectric materials" must have low leakage current through the gate dielectric material. Therefore, what we are hoping for is the development of new compositions and methods for depositing dielectric films having the desired higher dielectric properties. Due to the demand for dielectric films, it is important for materials with uniform coverage (this is a very high quality) for the performance of the gate dielectric material.

It is useful to deposit a metal film (having the general formula M _x Si _y N _z ) on a high-k film or a low-k film, which can be used as an electrode, such as a gate electrode, or as a carrier layer. . Typical processes for the growth of metal films include chemical vapor deposition, pulsed chemical vapor deposition, and atomic layer deposition methods. At the same time as the integrated circuit device is shrunk, the use of a metal-based dielectric film produces problems with the use of these materials and the compatibility of poly-Si, which is currently used as a gate electrode. Currently, a new generation of metal-based gate electrodes is believed to be used to overcome problems such as depletion, cross-contamination, and the like. In DRAM, this metal oxide material is currently used.

The use of a metal nitride ruthenium as a carrier layer sandwiched between a Cu interconnect or an electrode and a low-k dielectric film is an example of another application of a compound comprising a metal and ruthenium. The metal nitride has good electrical conductivity, and Cu can effectively prevent contamination of a low-k dielectric film. Furthermore, in terms of reducing RC hysteresis, the carrier layer The low resistance is very advantageous.

So far, a tantalum nitride film has been formed by CVD (using ammonia and a halogenated metal such as TiCl ₄ , TaCl ₅ ). However, this method requires a high thermal budget and a high process temperature (>650 ° C) and is not compatible with the back-end-of-line (BEOL) method.

In order to overcome such disadvantages, it is known from USP 6,602,783 that ammonia and an amino metal precursor (e.g., TDMAT, TDEAT, TBTDET, TAIMATA) can be used by CVD for the formation of metal nitride thin films. The use of such an amino metal precursor has been found to improve the film properties of, for example, CVD-TiSiN films. It has also been found that the use of an amino metal precursor, decane SiH ₄ , and ammonia by CVD to form a thin metal-doped metal nitride film is useful for improving carrier properties. However, SiH ₄ has a high vapor pressure and is pyrophoric, and any SiH ₄ leak causes safety problems. On the other hand, when dialkylaminodecane Si (NR ₁ R ₂ ) is used in place of decane as a source of ruthenium, there is a high possibility that a large amount of carbon is contained in the film, and the carrier layer is made Has an increased resistance.

Of particular importance is the formation of a metal oxynitride (MSiON) film, a metal silicate (MSiO), or a metal film (MSiN), which may be a metal nitride, a metal telluride, or a metal nitride. Forming a MSiON or MSiO dielectric material or a metal film, typically involving a metal source, a cerium source, an oxygen source, and a nitrogen source (collectively referred to herein as a precursor), to be appropriate The relevant amount is fed into a deposition apparatus in which a substrate is supported in a high temperature. The precursor system is formed to be fed into a deposition chamber through a "transport system". A "transport system" is used to measure and control the amount of various dielectric precursors being fed into the deposition chamber. A variety of different delivery systems are known to those skilled in the art. Once in the deposition chamber, the dielectric precursor reacts in a "forming" step and a dielectric film is deposited on the germanium substrate. One or more "forming" steps, as used in the present case, are the step of depositing the material on the substrate, or the step of modifying the molecular composition or structure of the film on the substrate. The "final composition of the film" of the film is the precise chemical composition and molecular structure of the layer after the final formation step is completed. Compounds of ruthenium, titanium, and tungsten, either as metal nitrides, metal halides, or metal nitrides, are the most promising carriers or electrode materials. The source of the metal used in the forming step is typically a liquid precursor or a liquid precursor solution comprising the desired metal in a solvent. Similarly, in the prior art of the present invention, the source of ruthenium available is the use of a liquid precursor comprising a desired ruthenium compound in a solvent.

For example, in Jpn. J. Appl. Phys., Vol. 42, No. 6A, pp. L578-580, June 2003; Applied Physics Letters, Vol. 80, No. 13, pp. 2362-2364, April 2002; U.S. Published Application No. 2003/0111678, No. 2003/0207549, No. 2003/0207549, or US Patent No. 06399208, Japanese Patent Application No. 2000272283, which discloses various manufacturing. A method of dielectric film. However, all of these films have one of the following or A variety of shortcomings.

Some gate dielectric formation methods require multiple formation steps. For example, in the first step, a dielectric film can be formed by depositing a metal and germanium on a substrate, followed by a second "post deposition step" in which the deposited metal is modified. The composition or structure of the film to achieve the desired final composition of the MSiON gate dielectric film. An example of a post deposition step is rapid thermal annealing in an environment filled with nitrogen or ammonia. Since the control of the composition of the film is important in the dielectric film deposition process, the less the number of steps, the better the control of the process, and the quality of the dielectric film (reaction in dielectric constant, density, pollution degree) The composition, composition, and other quality control conditions) and conformality (the ability of the film to deposit uniformly on all surfaces and shapes of the substrate) will be higher.

As is well known in the past, any source of ruthenium containing carbon in the ligand causes carbon to be produced in the film and degrades the electrical properties, either to enhance the leakage current for the insulating film or to reduce the conductivity of the metal film. . Furthermore, the chlorine contained in the film is not desirable because it would impair the electrical properties of the film, and also because of its stability in the film, since stability will result from the dielectric film. It is more difficult to remove chlorine. At the same time, chlorine is present in the ruthenium or metal source, producing chloride-based particles in the reaction chamber and deposited in the exhaust system. Therefore, to achieve the desired electrical characteristics, and to minimize the generation of particulates, and to minimize tool downtime due to the cleaning of the exhaust system, it is preferable to deposit from carbon in the atomic structure or A film of the precursor of chlorine.

The physical properties of a film can be modified by the ratio of metal (M) to germanium (Si) or (M/Si). It is hoped that the M/Si ratio is controlled over a wide range. Therefore, it is important to be able to vary the feed of metal and tantalum separately to achieve the widest possible M/Si ratio. Some methods use a source of precursors that contain some amount of pre-deposited metal. However, the change in feed rate of the precursor containing the metal ruthenium changes the total metal content fed to the process (due to the metal contained in the ruthenium precursor). This limits the controllability of the deposition process because the feed rate cannot be altered without changing the total amount of metal (the metal being fed into the deposition chamber). Still further, the M/Si ratio that can be fed is limited by the composition of the metal in the precursor of the cerium source. Therefore, variations in the desired M/Si ratio may require changes to the precursor solution being fed to the process.

The flow of the ruthenium precursors can also cause problems in the control of the film composition. Some methods in the art use an evaporator to evaporate the source of liquid helium. The evaporated stream is then fed into the deposition chamber. When the source of the metal and the source of the crucible are supplied in liquid form, both must be evaporated prior to introduction into the deposition chamber. Evaporation of two different flows produces a variable feed concentration and the formation of ruthenium or metal residues in the evaporator which can adversely affect the conformation of the film composition. The difference in evaporation of the ruthenium from the metal source can produce a compositional gradient among the dielectric materials.

Foaming a carrier gas through a liquid precursor also causes quality problems. In some methods, by using a carrier gas The bubbles are fed through a source of liquid helium. The evaporator is not used in these processes because the vapor pressure of the helium source is sufficiently high to be transported as a vapor in a mixture with a carrier gas. Among these methods, the flow transports the helium source into the deposition chamber, which can vary with temperature and pressure in the foaming system. The variability in the flow composition causes the compositional variability of the dielectric film, which is a serious quality problem.

For the above reasons, it is our hope to form a film with a final composition in a single forming step. Furthermore, the film should minimize the chlorine and carbon content of the molecular structure. It is also desirable to use a source of ruthenium that does not contain any deposited metal so that the feed from the ruthenium source and the feed from the source of the metal can be individually controlled. Finally, what we would like to have is a source of helium in the form of a gas phase under process feed conditions to avoid the need to evaporate a liquid helium source, or the need to bubble a carrier gas through a liquid source. .

Summary of the invention

It is an object of the present invention to provide a method and composition that meets the need to form a film that has excellent electrical quality and high conformality and that avoids the use of multiple forming steps to achieve uniform coverage and height. Conformal. Another object of the present invention is to provide a film which minimizes the chlorine and carbon content which both degrade the electrical properties of the film. Still another object of the present invention is to provide for controlling the M/Si ratio in the film over a wide range without changing the predecessor The ability of the solution. Still another object of the present invention is to avoid the quality and conformality that occurs when a liquid precursor (including multiple components) solution is evaporated, or when a carrier gas is bubbled through a liquid helium source. problem.

The film according to the present invention is formed by evaporating a source of metal and then at least one precursor (selected from a precursor from a group comprising: source of vaporized metal, source of germanium, The source of oxygen, and/or the source of nitrogen, is fed into a deposition apparatus and forms a film having the desired final composition in a single formation step. A post-deposition step is generally not required to achieve the desired final composition of the film.

According to a preferred embodiment of the invention, a gas phase ruthenium precursor and a liquid phase metal precursor are used for depositing a film having a stoichiometric stoichiometry. The gas phase ruthenium precursor must have sufficient volatility at a temperature above 15 ° C to supply the method as a vapor to avoid bubbling a carrier gas through a liquid or avoiding it in an evaporator. heating. This eliminates the control and quality problems associated with evaporation of two precursors (a metal containing a precursor and a precursor containing a precursor), or a bubble of a carrier gas through a liquid to source the source Feeding. Moreover, the gas phase ruthenium precursor is not classified as a metal that can independently control the feed of the metal source to the source of the ruthenium. Therefore, the M/Si ratio can be easily varied over a wide range without the need to mix a new precursor solution, and the method is not required to recalibrate the new mixture. Furthermore, the gas phase ruthenium precursor is carbon-free and chlorine-free, so it can dramatically reduce the effect of carbon and chlorine in the dielectric film. should. Finally, in accordance with the present invention, a dielectric film having the desired final composition is formed in a single step.

The metal source is typically a liquid precursor or a liquid precursor solution. The liquid phase precursor is injected into a system which vaporizes it into a gas phase. The precursor before the evaporation enters the deposition chamber, that is, the chamber where deposition occurs at a high temperature.

At the same time, the ruthenium precursor and the metal precursor are injected into a deposition chamber. According to an embodiment of the present invention, a mixture of inert gases such as nitrogen, argon, or the like, and the gas phase of the ruthenium precursor n may be used. The mixture preferably may comprise a precursor to inert gas ratio of between about 1/1000 vol. to about 1000/1 vol. In a preferred embodiment, the ruthenium precursor source is contained in the molecular structure of the ruthenium-derived compound and should be free of any carbon and chlorine, and/or metal atoms. The following molecular systems are examples of ruthenium precursors which can be used in accordance with the present invention:

(1) Trisilylamine:

(2) Disilylamine:

(3) Silylamine:

(4) Tridisilylamine:

(5) Aminodisilylamine:

(6) Tetrasilyldiamine:

(7) A dioxane derivative in which any one of H bonded to N may be substituted with SiH ₂ -SiH ₃ .

(8) Trioxane and its derivatives.

Gas containing oxygen and nitrogen can also be injected into the deposition chamber In the chamber, the deposition chamber has both a crystal evaporated metal precursor and a gas phase of the ruthenium precursor. In the preferred case, all molecules of the gas, as well as the introduced gas phase product, will be molecules free of carbon and or chlorine.

The precursor in the deposition chamber reacts to form a thin film on the substrate. The composition of the film can be precisely controlled by precisely controlling the flow rate of each precursor. The feed rate of the ruthenium and metal source is individually controllable, so that the M/Si ratio value of the final film can be controlled over a wide range without changing the source of the metal or the source of the ruthenium. Composition.

The reaction of the precursor in the deposition chamber forms a thin film with a desired final composition in a separate reaction step. After the dielectric deposit is deposited on the substrate, a post deposition step is not required, i.e., the composition of the dielectric film need not be modified by a single step.

Since the sources of helium, oxygen, and nitrogen in the present invention are all free of carbon and chlorine, the final film will have excellent properties, that is, a high dielectric constant for a gate dielectric material, or Excellent electrical conductivity for metal films.

A description of the preferred embodiment:

The present invention relates to a method and composition for forming an MSiON insulating film on a semiconductor substrate, and to a dielectric film produced according to the method. The invention is applicable to chemical vapor deposition as well as to atomic layer deposition methods, as well as to other methods familiar to those skilled in the art.

Referring to the MSiON method in Figure 2, the evaporation step 1 includes: steaming A source of metal is emitted to form a source of evaporated metal. A preferred embodiment of the metal source is a liquid phase precursor solution, preferably a dihydrocarbylamino group, an alkoxy group, or a hafnium (Hf), zirconium (Zr), titanium (Ti), niobium (Nb). ), 钽 (Ta), 钪 (Sc), 钇 (Y), 镧 (La), 釓 (Gd), 铕 (Eu), or 鐠 (Pr), or any inorganic element of the lanthanide (Ln) Compound. The liquid metal precursor solution is prepared and evaporated in a commercially available apparatus under suitable conditions known to those skilled in the art.

Referring again to the method of MSiON in Figure 2, during the feed step 2, the source of helium, the source of oxygen, and the source of nitrogen (collectively referred to herein as a dielectric precursor) are fed into the deposition chamber. Among them is the substrate (which needs to be deposited thereon) is placed under high temperature. The deposition chamber is typically maintained between about 300 and about 900 °C. In the preferred case, the surface of the workpiece will be between about 500 and 600 ° C in the deposition chamber. The feed of the dielectric precursor is effectively simultaneously occurring (atomic layer deposition involves high speed continuous pulses of the feed material, which for the purposes of the present invention are preferably effectively concurrent).

Referring to the MSiON method of Figure 2, during the feed step 2 of the MSiON method, the source of helium is injected into the deposition chamber in a controlled manner, effectively interacting with the evaporated metal source, and other media The electric precursor or the tantalum film element occurs simultaneously. In a preferred embodiment, the source of rhodium is present in the gas phase under process feed conditions. That is, a source of ruthenium in a preferred embodiment has a vapor pressure of greater than about 50 Torr at 20 ° C, which is sufficient for storage in the feed control system. There is no need for evaporation or foaming instruments in the delivery system. A preferred source of ruthenium, trimethyl decylamine can be stored as a liquid, but it has sufficient vapor pressure (more than 300 Torr vapor pressure at 25 ° C) to be present in the gas phase in the delivery system. There is no need to use an evaporator or a bubbler system. Since the source of the crucible belongs to the gas phase, it can be accurately measured and controlled using conventional means, and it is not subject to deposits or evaporation during evaporation during evaporation of the crucible or metal source. The vibration in the material condition is affected.

Referring again to the MSiON method of Figure 2, a preferred embodiment of the feed step 2 includes, but is not limited to, the use of a source of a source that does not contain carbon and/or chlorine in the molecular structure. Thus, the dielectric film has a minimum amount of carbon and chlorine contained therein, which results in the most desirable electrical characteristics.

Referring again to the MSiON method of Figure 2, a preferred embodiment of the feed step 2 includes, but is not limited to, feeding an oxygen and nitrogen source to the deposition chamber simultaneously with the source of the crucible Occurs (concurrently). Various preferred embodiments of the MSiON process use a source of nitrogen that does not contain carbon or chlorine in its molecular structure. It does not require nitrogen to be fed as a separate flow. The source of nitrogen can be the same as the source of the metal, the source of hydrazine or the source of oxygen. A preferred source of oxygen for the present invention is likewise free of carbon or chlorine in its molecular structure. Preferred embodiments include, but are not limited to, oxygen, nitrous oxide, and/or ozone as a source of oxygen. The nitrogen source is preferably selected from the group consisting of ammonia, dimethyl hydrazine alkylamine, formamylamine, tri-dimethyl hydrazine alkylamine, amino dimethyl hydrazine alkylamine, tetramethyl decyl diamine, and/or two A decane derivative in which any one of H can be substituted with NH ₂ and a mixture of any of the products in this group. Another preferred embodiment of the nitrogen source is trimethylammonium alkylamine. The oxygen and nitrogen sources are fed and controlled using a device well known to those skilled in the art.

The deposition and reaction of the dielectric precursor in the deposition chamber results in the formation of an MSiON film on the heated substrate during the formation step 3. A preferred embodiment of the MSiON film is a bismuth ruthenate film or a zirconium silicate film by using a metal source such as Hf(DEA) ₄ or Zr(DEA) ₄ or trimethyl decylamine. And a mixture of oxygen to form a bismuth or zirconium metal.

A preferred embodiment of the MSiON film is a hafnium oxynitride film or a zirconium oxynitride film, which is obtained by using a metal source such as Hf(DEA) ₄ or Zr(DEA) ₄ , A mixture of trimethyl decylamine, and oxygen, is formed by feeding cerium or zirconium metal.

Referring again to the MSiON method of Figure 2, the composition of the MSiON dielectric film can be controlled individually during the feed step 2 by varying the flow of each of the dielectric precursors. In particular, the feed rate of the ruthenium source and the metal source are independently controllable because the ruthenium source does not contain any deposited metal. Thus, the feed rate of the helium source can be varied independently of the feed rate of the metal source to affect the proportion of metal (M) and helium (Si) desired. Similarly, the metal source feed rate can be varied without affecting the feed rate of the helium source, and the M/Si ratio can also be varied. Due to the source and source of the metal The feed rate is independently controllable so that the M/Si ratio of the final dielectric film can be controlled over a wide range without altering the composition of the source and source of the metal.

Referring to the MSiON method of Figure 2, the dielectric precursor is fed into the deposition chamber, and in a single formation step 3, a dielectric film having the desired final composition is formed. After some or all of the dielectric deposits are deposited on the substrate to the desired final composition, a post-deposition step, ie a post-deposition step in which the composition or structure of the dielectric film is modified, is not required. .

According to another embodiment, the invention also relates to a method and composition for forming an MSiO insulating film on a semiconductor wafer. The invention is applicable to chemical vapor deposition as well as to atomic layer deposition methods, as well as to other methods familiar to those skilled in the art.

Referring to the MSiO process of Figure 3, it involves evaporating a source of metal to form a source of evaporated metal. A preferred embodiment of the metal source is a liquid phase precursor solution, preferably a dihydrocarbylamino group, an alkoxy group, or hafnium (Hf), zirconium (Zr), titanium (Ti), niobium (Nb). , 钽 (Ta), 钪 (Sc), 钇 (Y), 镧 (La), 釓 (Gd), 铕 (Eu), or 鐠 (Pr), or any of the lanthanide (Ln) inorganic compounds . The liquid metal precursor solution is prepared and evaporated in a commercially available apparatus under suitable conditions known to those skilled in the art.

Referring again to the method of MSiO in FIG. 3, during the feeding step 3, the source of cerium, the source of oxygen, and the source of nitrogen (collectively referred to herein as a dielectric precursor) are fed into a deposition chamber. Which is a substrate (required) To be deposited on it) placed under high temperature. The deposition chamber is typically maintained between about 300 and about 900 °C. In the preferred case, the surface of the workpiece will be between about 500 and 600 ° C in the deposition chamber. The feed of the dielectric precursor is effective to occur simultaneously (atomic layer deposition involves high speed continuous pulses of the feed material, which for the purposes of the present invention are preferably simultaneously effective).

Referring to the MSiO process of Figure 3, during the feed step 3 of the MSiO process, the source of helium is injected into the deposition chamber in a controlled manner, effectively interacting with the vaporized metal source, and other media. The electric precursor or the tantalum film element occurs simultaneously. In a preferred embodiment, one source is in the gas phase under process feed conditions. That is, a source of ruthenium in a preferred embodiment has a vapor pressure of greater than about 50 Torr at 20 ° C, which is sufficient to be present in the gas phase in the feed control system without the need for a delivery system. Evaporation or foaming equipment in the middle. A preferred source of ruthenium, trimethyl decylamine can be stored as a liquid, but it has sufficient vapor pressure (more than 300 Torr vapor pressure at 25 ° C) to be present in the gas phase in the delivery system. There is no need to use an evaporator or a bubbler system. Since the source of the crucible belongs to the gas phase, it can be accurately measured and controlled using conventional means, and it is not subject to deposits or evaporation during evaporation during evaporation of the crucible or metal source. The vibration in the material condition is affected.

Referring again to the MSiO process of Figure 3, a preferred embodiment of the feed step 2 includes, but is not limited to, the use of a source that does not contain carbon and/or chlorine in the molecular structure. Therefore, the dielectric thin The membrane has a minimum amount of carbon and chlorine contained, which results in the most desirable electrical properties.

Referring again to the MSiO process of Figure 3, a preferred embodiment of the feed step 2 includes, but is not limited to, feeding an oxygen and nitrogen source to the deposition chamber simultaneously with the source of the helium occur. Various preferred embodiments of the MSiO process use a source of nitrogen that does not contain carbon or chlorine in its molecular structure. It does not require nitrogen to be fed as an individual flow. The source of nitrogen can be the same as the source of the metal, the source of hydrazine or the source of oxygen. A preferred source of oxygen for the present invention is likewise free of carbon or chlorine in its molecular structure. Preferred embodiments include, but are not limited to, oxygen, nitrous oxide, and/or ozone as a source of oxygen. The best specific aspects include moisture. The oxygen and nitrogen sources are fed and controlled using a device well known to those skilled in the art.

Referring again to the MSiO method of Figure 3, the deposition and reaction of the dielectric precursor in the deposition chamber results in the formation of an MSiO film on the heated germanium substrate during the formation step 3. A preferred embodiment of the MSiO film is a bismuth ruthenate film or a zirconium silicate film by using a metal source such as Hf(DEA) ₄ or Zr(DEA) ₄ or trimethyl decylamine. a mixture of water, gas, and oxygen to form a bismuth or zirconium metal.

Referring again to the MSiO process of Figure 3, the composition of the MSiO dielectric film can be controlled individually during the feed step 2 by varying the flow of each of the dielectric precursors. In particular, the feed rate of the helium source and the metal source are independently controllable because of the source of the helium Does not contain any deposited metals. Thus, the feed rate of the helium source can be varied independently of the feed rate of the metal source to affect the proportion of metal (M) and helium (Si) desired. Similarly, the metal source feed rate can be varied without affecting the feed rate of the helium source, and the M/Si ratio can also be varied. Since the feed rate of the ruthenium source and the metal source is independently controllable, the M/Si ratio of the final dielectric film can be controlled over a wide range without changing the composition of the ruthenium source and the metal source. .

Referring to the MSiO method of FIG. 3, the dielectric precursor is fed into the deposition chamber, and in a single formation step 3, a dielectric film having a desired final composition is formed. After some or all of the dielectric deposits are deposited on the substrate to the desired final composition, a post-deposition step, ie a post-deposition step in which the composition or structure of the dielectric film is modified, is not required. .

The ruthenium precursor of the ruthenium source is preferably a list similar to the ruthenium precursors disclosed above.

According to another embodiment, the invention also relates to a method and composition for forming an MSiN insulating film on a semiconductor wafer. The invention is applicable to chemical vapor deposition as well as to atomic layer deposition methods, as well as to other methods familiar to those skilled in the art.

Referring to the MSiN method of Figure 5, the evaporation step 1 involves evaporating a source of metal to form an evaporated source of metal. A preferred embodiment of the metal source is a liquid phase precursor solution, preferably a dihydrocarbylamino group, an alkoxy group, or hafnium (Hf), zirconium (Zr), titanium (Ti), niobium (Nb). , An inorganic compound of lanthanum (Ta), strontium (Sc), yttrium (Y), lanthanum (La), lanthanum (Gd), lanthanum (Eu), or praseodymium (Pr), or any lanthanide (Ln). The liquid metal precursor solution is prepared and evaporated in a commercially available apparatus under suitable conditions known to those skilled in the art.

Referring again to the method of MSiN in FIG. 5, during the feed step 2, a source of helium, a source of oxygen, and a source of nitrogen (collectively referred to herein as a dielectric precursor) are fed into a deposition chamber. Where the substrate (which needs to be deposited thereon) is placed under high temperature. The deposition chamber is typically maintained between about 300 and about 900 °C. In the preferred case, the surface of the workpiece will be between about 500 and 600 ° C in the deposition chamber. The feed of the dielectric precursor is effective to occur simultaneously (atomic layer deposition involves high speed continuous pulses of the feed material, which for the purposes of the present invention are preferably simultaneously effective).

Referring to the MSiN method of FIG. 5, during the feed step 2 of the MSiN method, the source of the helium is injected into the deposition chamber in a controlled manner, effectively interacting with the vaporized metal source, and other media. The electric precursor or the tantalum film element occurs simultaneously. In a preferred embodiment, one source is in the gas phase under process feed conditions. That is, a source of ruthenium in a preferred embodiment has a vapor pressure of greater than about 50 Torr at 20 ° C, which is sufficient to be present in the gas phase in the feed control system without the need for a delivery system. Evaporation or foaming equipment in the middle. A preferred source of hydrazine, trimethyl decylamine can be stored as a liquid, but it has sufficient vapor pressure (more than 300 Torr vapor pressure at 25 ° C) at which The delivery system is present in the gas phase without the use of an evaporator or bubbler system. Since the source of the crucible belongs to the gas phase, it can be accurately measured and controlled using conventional means, and it is not subject to deposits or evaporation during evaporation during evaporation of the crucible or metal source. The vibration in the material condition is affected.

Referring again to the MSiN method of Figure 5, a preferred embodiment of the feed step 2 includes, but is not limited to, the use of a source of a source that does not contain carbon and/or chlorine in the molecular structure. Thus, the dielectric film has a minimum amount of carbon and chlorine contained therein, which results in the most desirable electrical characteristics.

Referring again to the MSiN method of Figure 5, a preferred embodiment of the feed step 2 includes, but is not limited to, feeding an oxygen and nitrogen source to the deposition chamber, simultaneously with the source of the crucible occur. Various preferred embodiments of the MSiN method use a source of nitrogen that does not contain carbon or chlorine in its molecular structure. It does not require nitrogen to be fed as a separate flow. The source of nitrogen can be the same as the source of the metal, the source of cerium or the source of oxygen. A preferred source of oxygen for the present invention is likewise free of carbon or chlorine in its molecular structure. Preferred embodiments include, but are not limited to, oxygen, nitrous oxide, and/or ozone as a source of oxygen. The nitrogen source is preferably ammonia. Another preferred embodiment of the nitrogen source is trimethylammonium alkylamine. The oxygen and nitrogen sources are fed and controlled using a device well known to those skilled in the art.

Referring again to the MSiN method of Figure 5, the deposition and reaction of the dielectric precursor in the deposition chamber results in the formation of an MSiON film on the heated substrate during the formation step 3. A preferred embodiment of the MSiN film is a tantalum nitride film or a titanium nitride film by using a metal source such as TaCl ₅ , TiCl ₄ , Ta(DMA) ₅ , or Ti ( DEA) ₄ ), and a mixture of trimethyl decylamine to form a ruthenium or zirconium metal.

Referring again to the MSiN method of Figure 3, the composition of the MSiN dielectric film can be controlled individually during the feeding step 2 by varying the flow of each of the dielectric precursors. In particular, the feed rate of the ruthenium source and the metal source are independently controllable because the ruthenium source does not contain any deposited metal. Thus, the feed rate of the helium source can be varied independently of the feed rate of the metal source to affect the proportion of metal (M) and helium (Si) desired. Similarly, the metal source feed rate can be varied without affecting the feed rate of the helium source, and the M/Si ratio can also be varied. Since the feed rate of the ruthenium source and the metal source is independently controllable, the M/Si ratio of the final dielectric film can be controlled over a wide range without changing the composition of the ruthenium source and the metal source. .

Referring to the MSiN method of FIG. 5, the dielectric precursor is fed into the deposition chamber, and in a single formation step 3, a dielectric film having a desired final composition is formed. After some or all of the dielectric deposits are deposited on the substrate to the desired final composition, a post-deposition step, ie a post-deposition step in which the composition or structure of the dielectric film is modified, is not required. .

According to this specific aspect, the source of nitrogen and nitrogen is similar to the above. Revealed sources.

Example 1

This embodiment relates to the manufacture of yttrium oxynitride.

The CVD tool used in this embodiment is illustrated in FIG. In FIG. 6, a wafer 1 is mounted in a CVD chamber 11, the CVD chamber 11 has a heater around it, and the desired film is formed on the wafer 1 On the surface. The CVD chamber 11 is evacuated by means of a pump 12. In this example, the metal precursor Hf(NEt ₂ ) ₄ (tetrakisdiethylaminohafnium) is stored in a liquid container 21. Helium 22 is used as a carrier gas for the Hf(NEt ₂ ) ₄ . Hf(NEt ₂ ) ₄ in the liquid container 21 is transported by the pressure of the crucible 22 through a liquid mass flow controller 23 and into an evaporating gas 25. Helium 22 is also conveyed through a mass flow controller 24 and into an evaporating gas 25. Hf(NEt ₂ ) ₄ , which is contending by the vaporizing gas 25, is fed into the CVD chamber 11 with He. Trimethyldecylamine (TSA) is supported in a bottle 31 and the TSA is conveyed through a mass flow controller 32 into the CVD chamber 11. A line for nitrogen gas 33 is connected along the path of the TSA line, and nitrogen gas 33 is fed along the CVD chamber 11 and the TSA. Oxygen 41 (oxidant) is fed through a mass flow controller 42 and into the CVD chamber 11. Using a CVD tool as described, a yttrium oxynitride film was produced under the following conditions.

Mode 1-1

Pressure = 0.35 Torr, temperature = 500 ° C, Hf (NEt ₂ ) ₄ flow rate = 0.5 sccm, He flow rate = 180 sccm, TSA flow rate = 4 sccm, O ₂ flow rate = 40 sccm, N ₂ flow rate = 25 sccm.

Using this set of conditions, at a film formation rate of 135 Å/min, yttrium oxynitride having a composition ratio of Hf/Si = 5:1 and O/N = 3:1 was obtained.

Mode 1-2

Pressure = 0.35 Torr, temperature = 400 ° C, Hf (NEt ₂ ) ₄ flow rate = 0.5 sccm, He flow rate = 180 sccm, TSA flow rate = 4 sccm, O ₂ flow rate = 40 sccm, N ₂ flow rate = 25 sccm. This mode is the same as mode 1-1 except that the temperature is lowered to 400 °C.

Using this set of conditions, at a film formation rate of 72 Å/min, yttrium oxynitride having a composition ratio of Hf/Si = 6.6:1 and O/N = 4:1 was obtained.

Mode 1-3

Pressure = 1.0 Torr, temperature = 300 ° C, Hf (NEt ₂ ) ₄ flow rate = 0.5 sccm, He flow rate = 180 sccm, TSA flow rate = 4 sccm, O ₂ flow rate = 100 sccm, N ₂ flow rate = 500 sccm.

Using this set of conditions, yttrium oxynitride was obtained at a film formation rate of 30 Å/min. In this case, the composition of yttrium oxynitride is O/N = 13:1, and a trace amount of ruthenium.

Example 2

This embodiment relates to the manufacture of cerium oxide.

The CVD tool used in this embodiment is illustrated in FIG. The CVD tool of Figure 7 has a structure very similar to the CVD tool of Figure 1, which differs from the latter in that it provides a H ₂ O filled bubbler 43 along the path of the O ₂ gas 42 line. This causes H ₂ O to be introduced into the CVD chamber 11 in accordance with O ₂ which is an oxidizing agent. Using a CVD tool as described, a yttrium oxynitride film was produced under the following conditions.

Mode 2-1

Pressure = 0.5 Torr, temperature = 400 ° C, Hf (NEt ₂ ) ₄ flow rate = 0.5 sccm, He flow rate = 160 sccm, TSA flow rate = 4 sccm, O ₂ flow rate = 40 sccm, H ₂ O flow rate = 1.2 sccm, N ₂ flow rate = 20sccm.

Using this set of conditions, at a film formation rate of 135 Å/min, yttrium oxide having a composition ratio of Hf/Si = 3.5:1 (C below the detection limit) was obtained.

Example 3

This embodiment is related to the fabrication of a titanium nitride film doped with antimony.

The CVD tool used in this embodiment is illustrated in FIG. In FIG. 8, a wafer 1 is mounted in a CVD chamber 11 having a heater around the CVD chamber 11 and the desired film is formed on the wafer 1 On the surface. The CVD chamber 11 is evacuated by means of a pump 12. In this example, the metal precursor titanium tetrachloride (TiCl ₄ ) is supported in the bubble 51 and the TiCl ₄ vapor is fed into the CVD chamber 11. Trimethyldecylamine (TSA) is supported in a bottle 31 and the TSA is conveyed through a mass flow controller 32 into the CVD chamber 11. The gas system discharged from the CVD chamber 11 is discharged from passing through an absorber 13. Using the CVD tool described, a titanium nitride film doped with antimony was produced under the following conditions.

Mode 3-1

Pressure = 1 Torr, temperature = 625 ° C, TiCl ₄ flow rate = 5 sccm, TSA flow rate = 4 sccm, N ₂ flow rate = 20 sccm, time = 15 minutes.

According to the AES analysis, the final film is a titanium nitride having a stoichiometric composition containing a trace amount of ruthenium. This film is approximately 4000 Å thick. The film formation rate is approximately 270 Å/min.

Mode 3-2

Pressure = 1 Torr, temperature = 550 ° C (this film formation temperature is substantially lower than the film formation temperature of TiCl ₄ /NH ₃ used in the prior art), TiCl ₄ flow rate = 5 sccm, TSA flow rate = 4 sccm, N ₂ flow rate = 20sccm, time = 15 minutes.

According to the AES analysis, the final film is a titanium nitride having a stoichiometric composition containing a trace amount of ruthenium. This film is approximately 290 Å thick. The film formation rate is approximately 19 Å/min.

Example 4

Atomic layer deposition from Hf(NEt ₂ ) ₄ , ozone, and HfSiO of TSA instead of pulses.

P=0.5 Torr, T=350°C

Hf(NEt ₂ ) ₄ (0.25 sccm) with carrier gas (N ₂ : 25 sccm): 7 seconds

TSA (1 sccm): 3 seconds

O ₃ (2.5 sccm) mixed with O ₂ (50 sccm): 5 seconds

N ₂ : 70 sccm (continuous)

Obtained under these experimental conditions is the deposition of cerium oxide (Hf _0.75 Si _0.05 O ₂ ).

Example 5

Deposition of TaN from TaCl ₅ and TSA (CVD)

Furnace: 500C-1 Torr (the reactor is in the form of a hot wall)

FR TSA: 5 sccm (FR: flow rate)

FR NH ₃ : 20 sccm

FR TaCl ₅ : 5 sccm (+FR N ₂ carrier gas: 20 sccm)

10 minute deposition

What is obtained is the deposition of tantalum nitride with a trace amount of antimony.

Example 6

Atomic layer deposition of TaN from TaCl ₅ and TSA

Reactor: 150C, Susceptor: T = 300 C-P = 2 Torr (The reactor is in the form of a cold wall, that is, the wafer is deposited through a susceptor below)

FR TSA: 1 sccm

FR TaCl ₅ : 0.5 sccm (+FR Ar carrier gas: 42 sccm)

40 cycles

What is obtained is the deposition of tantalum nitride with a trace amount of antimony.

Although the present invention has been described in considerable detail and reference to certain preferred forms thereof, other forms are possible. Lift For example, the composition and method can be practiced in addition to chemical vapor deposition or atomic layer deposition methods. In addition, the deposition of the dielectric film can be accomplished under varying temperatures and conditions. Still further, the invention can include a variety of metal, germanium, and germanium sources as are well known in the art. Therefore, the spirit and scope of the appended claims are not limited by the description of the preferred forms included herein. The inventors intend to include all modifications, equivalents, and alternatives falling within the spirit and scope of the invention, as defined by the appended claims.

1‧‧‧矽 wafer

11‧‧‧ CVD chamber

12‧‧‧ pump

13‧‧‧ absorber

21‧‧‧Liquid container

22‧‧‧He gas

23‧‧‧Liquid mass flow controller

24‧‧‧Flow Controller

25‧‧‧evaporation gas

31‧‧‧ bottles

32‧‧‧Flow Controller

33‧‧‧N ₂ gas

41‧‧‧O ₂ gas

BRIEF DESCRIPTION OF THE DRAWINGS Figure 1 is a flow diagram of a prior art method for forming a layer of MSiON insulating film.

2 is a flow chart showing the steps of a method for forming a layer of MSiON insulating film in accordance with the present invention.

Figure 3 is a flow chart showing the steps of a method for forming a layer of MSiO insulating film in accordance with the present invention.

4 is a flow chart of a prior art method for forming a layer of MSiN metal film.

Figure 5 is a flow diagram of the steps of a method for forming a layer of MSiN metal film in accordance with the present invention.

Fig. 6 is a schematic view showing a gas distribution system of a CVD tool used in Example 1 of the present invention.

Fig. 7 is a schematic view showing a gas distribution system of a CVD tool used in Example 2 of the present invention.

Figure 8 is a CVD tool used in Example 3 of the present invention. The structural pattern of the gas distribution system.

1‧‧‧矽 wafer

11‧‧‧ CVD chamber

12‧‧‧ pump

13‧‧‧ absorber

21‧‧‧Liquid container

22‧‧‧He gas

23‧‧‧Liquid mass flow controller

24‧‧‧Flow Controller

25‧‧‧evaporation gas

31‧‧‧ bottles

32‧‧‧Flow Controller

33‧‧‧N ₂ gas

41‧‧‧O ₂ gas

Claims (18)

A method of forming a MSiON or MsiO dielectric film, the method comprising: evaporating a metal source (M) to form an evaporated metal source; feeding a plurality of precursors into a deposition apparatus, wherein the precursor comprises The evaporated metal source, cerium source, oxygen source, and nitrogen source, if desired, MSiON; and forming a dielectric film, wherein the dielectric film is formed using the desired final composition without a post-deposition step . A method of forming a metal thin film of MSiN, comprising the steps of: evaporating a metal source to form an evaporated metal source; feeding a plurality of precursors to a deposition apparatus, wherein the precursor comprises the evaporated metal source And a source of nitrogen; and forming a dielectric film, wherein the dielectric film is formed using the desired final composition without a post-deposition step. The method of claim 1 or 2, wherein the source of the ruthenium comprises a molecular structure that does not comprise carbon and/or a molecular structure that does not comprise chlorine. The method of claim 1 or 2, wherein the source of the hydrazine is a gas phase. The method of claim 1 or 2 wherein the source of hydrazine is below 20 ° C and has a vapor pressure of at least 50 Torr. The method of claim 1 or 2, wherein the source of the hydrazine is selected from the group consisting of dioxane, trimethyl decylamine, dimethyl hydrazine alkylamine, formamylamine, tris-dimethyl hydrazine alkylamine, Aminomethyl dimethyl hydrazine, tetramethyl hydrazine A group consisting of alkyl diamines, dioxane, dioxane and/or derivatives of trioxane, and mixtures thereof. The method of claim 1 or 2, wherein the source of oxygen comprises a molecular structure that does not comprise carbon and/or a molecular structure that does not comprise chlorine. The method of claim 1 or 2, wherein the source of oxygen is selected from the group consisting of oxygen, nitrous oxide, ozone, dioxane, and mixtures thereof. The method of claim 1 or 2, wherein the source of nitrogen comprises a molecular structure that does not comprise carbon and/or a molecular structure that does not comprise chlorine. The method of claim 1 or 2, wherein the source of nitrogen is the same as the source of the metal, the source of the ruthenium, and/or the source of oxygen. The method of claim 1 or 2, wherein the nitrogen source is ammonia. The method of claim 1 or 2, wherein the source of the metal is selected from the group consisting of dialkylamino groups and/or alkoxy ligands. The method of claim 1 or 2, wherein the metal source is an inorganic compound selected from the group consisting of hafnium (Hf), zirconium (Zr), titanium (Ti), niobium (Nb), and tantalum (Ta). ), 钪 (Sc), 钇 (Y), 镧 (La), 釓 (Gd), 铕 (Eu), 鐠 (Pr), or any other lanthanide (Ln), and mixtures thereof In the group. The method of claim 1 or 2, wherein in the final composition of the dielectric film, the source of the metal and the source of the ruthenium are independently controllable. The method of claim 1 or 2, wherein the dielectric film is completed by using a chemical vapor deposition method. The method of claim 1 or 2, wherein the dielectric film step is performed by using an atomic layer deposition method. An MSiON or MSiO dielectric film obtained by the method according to any one of claims 1 and/or 3 to 16. An MSiN metal film obtained by the method according to any one of claims 2 to 16.