TWI281216B - Sequential reducing plasma and inert plasma pre-treatment method for oxidizable conductor layer - Google Patents

Abstract

A method for forming a barrier layer upon a copper containing conductor layer employs a hydrogen containing plasma treatment of the copper containing conductor layer followed by an argon plasma treatment of the copper containing conductor layer. The barrier layer may be formed employing a chemical vapor deposition method, such as an atomic layer deposition method. When the deposition method employs a metal and carbon containing source material, the two-step plasma pretreatment provides the barrier layer with enhanced electrical properties.

Description

1281216 IX. DESCRIPTION OF THE INVENTION: TECHNICAL FIELD OF THE INVENTION The present invention relates to a method of manufacturing a microelectronic product, which is related to the removal of an oxide conductor layer in the manufacture of a microelectronic product. [Prior Art] A microelectronic product is a method in which a plurality of patterned conductor layers are formed on a substrate, and dielectric layers are separated by dielectric layers. When the degree of integration of microelectronic products is higher, it is becoming more and more popular to manufacture microelectronic products using patterned copper containing a layer of conductive material, which is a dielectric layer with a low dielectric constant. Isolation. In the case of microelectronics, copper containing conductive materials is often used to provide improved conductivity. The so-called low-k dielectric material refers to a dielectric material having a dielectric constant of less than about 4, and the use of these low dielectric constant dielectric materials can reduce the interference between the conductor layers of each other. Although the use of copper and low dielectric constant dielectric materials containing conductive materials is quite common in the manufacture of microelectronic products, it is not entirely problem free. In particular, in the manufacture of microelectronic products, the preparation of copper containing electrically conductive materials is quite disadvantageous for diffusion in dielectric materials of low dielectric constant. In addition, since a low dielectric constant dielectric material has a fragile mechanical property, copper containing a conductive material is susceptible to intrusion and oxidation. The limitations of the above materials often affect the performance of the electrical and reliability of microelectronic products. Therefore, there is a need for a microelectronics 1281216 95. a product that has improved electrical and reliability performance, and the copper is used in the electronic product system to contain conductive materials by using a low dielectric constant. Electrical material for conductor layer isolation. The purpose of the invention. SUMMARY OF THE INVENTION The first object of the present month is to provide a method for manufacturing a microelectronic product, wherein the microelectronic product has a picture (4) of copper comprising a layer of a conductive material, and each of the layers of the conductive material is dielectrically bonded by a low dielectric constant. The layers of material are isolated from each other. A second object of the present invention is the method according to the first aspect of the present invention, wherein the microelectronic product produced has improved electrical and achievable performance. According to the purpose of the present invention, the present invention provides a method of manufacturing a microelectronic product. According to an embodiment of the invention, a substrate is first provided. A copper layer containing a conductor layer is formed on the substrate. Next, the (four) (four)-hydrogen-containing plasma of the (four) layer is treated, and the copper containing the conductor layer after the treatment with hydrogen (four) is used. Finally, the copper containing the conductor layer after the treatment with the hydrogen-containing plasma is further processed through the argon-containing (four) row to form the copper of the conductor-containing layer after the first (four)-through. Next, a second conductor layer, such as a conductor barrier layer, is formed over the fully processed copper layer containing the conductor layer to process the microelectronic product. This second conductor layer can be formed by a method of prosthesis, such as chemical vapor deposition or, more particularly, atomic layer deposition, a metal of a volatile metal and a volatile raw material. This last formed second conductor layer has the electrical characteristics of the cover 1281216, thus providing better confidence in the microelectronics. In a typical embodiment, the primary object of the present invention is to provide a method of cleaning a oxidized conductor layer using a continuous reduction plasma and a blunt plasma treatment. Then, the second conductor layer can be formed above the oxidation conductor layer after the series electropolymerization treatment, and the second conductor layer is formed by chemical vapor deposition, such as atomic layer deposition, using metal and volatile raw materials. When the stone is formed, the second conductor layer formed at the end has the electrical property and reliability of the cover. The method of the present invention contemplates a microelectronic σα ° manufactured according to the method of the present invention. The present invention provides a method of fabricating a microelectronic product, wherein the microelectronic product: patterned copper having a layer of conductive material, and each conductive material The layers are isolated from each other by a layer of low dielectric constant dielectric material, and the microelectronic product has improved reliability performance. In order to achieve the above object, in the case of copper in a layer of W conductive material in a microelectronic product, a hydrogen-containing electropolymerization (usually a low plasma j treatment followed by an argon-containing plasma) is used. (usually a blunt gas plasma). After a series of plasma treatments, a first conductor layer, such as a conductor barrier layer, is deposited over the fully processed copper layer of the conductor layer. In order to make the second conductor layer have an improved conductivity, the second conductor layer is formed by chemical vapor deposition, atomic layer deposition, and using metal and carbon containing volatile raw materials. The method of the invention is particularly useful when formed.

1281216 [Embodiment] The present invention provides a method of manufacturing a microelectronic product, wherein the microelectronic product has patterned copper comprising a layer of conductive material, and each layer of conductive material is isolated from each other by a layer of low dielectric constant dielectric material In order to enhance the electrical and credibility of microelectronic products. In a specific embodiment, in order to achieve the above object, the copper containing the conductive material layer in the microelectronic product is treated with a hydrogen-containing plasma followed by an argon-containing plasma. deal with. After the series of plasma treatments, a second conductor layer, such as a conductor barrier layer, is deposited over the fully processed copper containing conductor layer for use in the microelectronics. The second conductor layer has improved electrical conductivity and reliability. In a typical embodiment, the present invention utilizes a reducing plasma and a blunt plasma to treat an oxidized conductor layer. Then, a second conductor layer can be formed over the series of plasma-treated oxide conductor layers, and the second conductor layer formed has improved electrical characteristics and reliability. Figures 1 through 6 show a series of schematic cross-sectional views of each of the steps of fabricating a microelectronic product in accordance with a preferred embodiment of the present invention. Figure 1 shows a schematic cross-sectional view of the initial stage of manufacturing a microelectronic product. Rong 1 The door shows a substrate 10. A conductor layer-containing pattern copper 12 is formed therein and a dual damascene aperture 11 is a portion of the conductor layer patterned steel 12. The double-hole U is defined by the following structure: (1) a pair of patterned first barrier layers 14 a 1281216 95·

El for the page change and 14b; (2) - for the patterned first dielectric layers i6a and 16b, formed and arranged on the first patterned barrier layers 14a and 14b; (3) - the pattern The remaining stop layers 18a and 18b are formed and arranged on the pair of patterned dielectric layers 16a and 16b; (4) a pair of patterned second dielectric layers 20a and 20b are formed and formed Embedded in the patterned etch stop layers i8a and 18b' side by side in a row; (5) a pair of patterned flat stop layers 22a and 22b' formed and arranged in the pair of patterned second dielectric layers 2 〇a and 2〇b

on. The substrate 1 使用 used in the microelectronic product is selected from the group consisting of an integrated circuit of a ceramic substrate and a photovoltaic substrate product, but is not limited thereto. Generally, the substrate 1 The crucible includes a semiconductor substrate. The first conductor-containing patterned copper 12 may be formed of copper or a copper alloy. Generally, the first conductor-containing patterned copper 12 has a line width of about micrometers to 10 micrometers and a thickness of about 4000 angstroms to 8,000 angstroms.

The patterned first dielectric layers 16a and 16b, and the patterned second dielectric layers 20a and 20b may be formed using any dielectric material. Such a dielectric layer = a dielectric material having a generally high dielectric constant, that is, an electrical material having a dielectric constant higher than 4, for example, a oxidized oxide dielectric material and a nitride dielectric material, but not limited thereto . Such a dielectric layer may also comprise a dielectric material having a generally low dielectric constant, that is, a dielectric material having a dielectric constant lower than 4, for example, a spin-on glass (SPin_〇n_Glass) dielectric material, a spin coating type. Polymer (Spin-〇np〇lymer) dielectric material, fluoride glass (fWosilicate glass); tantalum electrical material and amorphous carbon _〇η) dielectric material, but not limited to this. 1281216

11 3 ο月曰修(more) replacement page when the patterned first dielectric layers 16a and 16b are paired with the patterned second electrical layers 20a and 20b, with a relatively low dielectric constant When the electrical material is formed, the patterned first _ barrier layer 14_(10) pair, the patterned surname stops | l8a and 18b pairs and the patterned flat stop layer ❿ # 22b pair each, generally A high dielectric constant dielectric material is formed. - In general, (1) the patterned first barrier layer i4a and i4b are centered, forming a thickness of about angstrom to lake ang; (7) patterning the first dielectric layer 16M port l6b is centered Each thickness of the film is about 4 angstroms to angstroms; (3) the patterning of the remaining layers 18a and 18b is the center of the pair, forming a thickness of about 2 angstroms to 5 angstroms. (4) The second dielectric layer 20M of the meshed dielectric layer 20M, each of the 2 〇b pairs is formed to have a thickness of about 4,000 angstroms, and (3) a patterned flat stop layer a. And 22b, each of which has a thickness of about 200 angstroms to 500 angstroms. The =2 figure shows the result of forming a series of = side gaps „ 24 on the side surfaces of the double inlaid holes u. This series of selective sides = soil layer 24, generally with deposition and non-isotropic (4) The method of engraving is to form the form = these formation methods are traditional in the manufacturing technology of microelectronic products. This series of selective side spacer layers 24 are generally formed by high dielectric two C electricity. , L material m 弟 ^ 展示 展示 展示 使用 使用 使用 — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — 含 含 含 含 含After the treatment of 26, it will form - after the treatment with hydrogen-containing plasma, 11 1281216 Γ - force. 胗 (3⁄4 正杂页) containing the conductor layer of copper 12, in general, by this hydrogen-containing electropolymerization 26 The treatment process is mainly used to chemically reduce or eliminate the oxide residue formed on the patterned layer 12 containing the conductor layer. # The condition for supplying the hydrogen-containing electricity m 26 is: (1) the pressure of the reaction chamber is about i to 100 mtorr ( Taur); (2) The energy of the radio wave source is about 1 〇〇 to ι〇〇〇瓦, and the energy is about 1〇〇 to 1000 watts; (3) a substrate having a patterned layer of copper ruthenium 2 having a temperature of about 1 to 2 degrees Celsius; (4) a hydrogen flow rate of about 1 to 0 to 5,000 standard cubic centimeters per minute (standard cubic

Centimeters Per Minute, SCCM); and (5) processing time is approximately ι〇 to 200 seconds. The hydrogen-containing plasma can also be used with other types of reducing gases such as ammonia. Figure 4 is a graph showing the results of processing the microelectronic product of Figure 3 using an argon-containing plasma 28. The conductive layer patterned copper 12' after being treated with hydrogen plasma is further processed through an argon-containing plasma 28 to form a conductor layer containing copper 12 after treatment with hydrogen and argon containing plasma, This can be regarded as the copper containing conductor layer after the full plasma treatment. In a subsequent example, the patterned copper layer 12 containing the conductor layer after hydrogen-containing plasma treatment, after treatment with an argon-containing plasma 28, provides an excellent surface condition for use. A conductor layer, such as a conductor barrier layer, is formed to provide excellent electrical properties. The conditions for providing the argon-containing plasma 28 are as follows: (1) the pressure in the reaction chamber is about 10 〇 〇 rr (Tayl); (2) the energy of the radio wave source is about 6 〇〇 to 8 〇〇 ( Preferably, the energy system is from about 650 to 750 watts, a bias energy is about 1 〇 to 100 watts (and the preferred energy is about 20 to 50 watts); (3) a substrate, 12 1281216 is repaired (more) The patterning copper 12 containing the conductor layer after being treated with the tantalum plasma is replaced by a temperature of about 10 to 200 degrees Celsius; (4) the flow rate of the argon gas is about 1 to 2 〇 SCCM (and preferably The flow rate is from about 5 to 1 〇 SCCM); and (5) the processing time is about i to 20 seconds (and the preferred processing time is about 5 to 1 sec). The above processing conditions are generally used to provide a "soft, argon plasma to treat a patterned layer of copper 12 after treatment with a hydrogen-containing plasma. Other types may also be used.

Passive gas plasmas, such as helium, neon, xenon, and krypton, are not limited to this. Figure 5 shows the microelectronics in Figure 4, particularly in a dual damascene hole and in contact with a copper-containing conductor layer 12'' after treatment with hydrogen and argon-containing plasma to form a The result of the blanket barrier layer 3 (). Figure # also shows a second copper 32 of a blanket-like conductor layer formed over the blanket barrier layer 30.

The blanket barrier layer 30 is a blanket conductor barrier layer that can be formed using any method and material. The blanket barrier layer 3 can be formed by physical vapor deposition, chemical vapor deposition, and atomic layer deposition (which can be regarded as a digital chemical vapor deposition method). The blanket barrier layer 3 can be formed using a barrier material of a conductor, such as tungsten, titanium, a button, and a nitride thereof, but is not limited thereto. Preferably, the blanket barrier layer 3 is formed using a nitride nitride conductor barrier material, which uses a penta-dimethylamino-tantalum (Ta((CH3)2N)5) as a gas phase. Metal and one carbon raw materials are formed by atomic layer deposition. The conditions of the atomic layer deposition method are as follows: (1) in the absence of plasma activation, the reaction chamber pressure is about 1 to 10 mtorr (Tayl); (2) - the substrate 10, including a 13 1281216

9¥T 日修(more) is replacing the page containing copper and 12 with conductor layer treated with hydrogen and argon-containing plasma, and the temperature is about 100 to 200 degrees; (3) pentadimethylamine The group source, in the case of carrier gas = rate about 'Ο to 2000 SCCM, its material concentration is about 至5 to i volume hundred-minute. In general, the blanket barrier layer 3 is formed to a thickness of about 5 Å to 5 Å. The atomic layer deposition method uses a stepwise deposition of the above-mentioned stepped source material and selectively performs a step gas treatment to provide a nitrogen layer. • Recording the second copper 32' of the conductor layer is generally formed by a method or material similar to, similar or identical to the formation of the patterned copper 12 with a conductor layer. 32 is formed to a thickness of about 1000 to 8000 angstroms. Figure 6 is a view showing the result of flattening the blanket-like conductor layer second copper 32 and the blanket barrier layer 30, which is formed on the patterned barrier layer 3a to form a patterned second copper 32a containing a conductor layer. And contacting the conductor-containing layer copper 12, which is treated with chlorine and argon-containing plasma in one of the double-inserted holes, in contact with each other. This flat _ 4 method can use the methods conventionally used in the art of manufacturing microelectronics, particularly such as chemical mechanical polishing. Figure 6 shows a schematic cross-sectional view of a microelectronic product made in accordance with a preferred embodiment of the present invention. The microelectronic product includes a conductor layer-patterned copper- 12", a barrier layer formed thereon, and a patterned second copper 32a including a conductor layer, wherein the conductor layer is patterned second The copper 32a is formed on the barrier layer of the microelectronic product, and the patterned second copper layer and the patterned barrier layer 3〇a formed on the conductor layer including the conductor layer patterned copper-12" have Improved electrical properties, such improved electrical properties 14 1281216 I IL · 〇V;

I Feng-Xiu (more) is replacing page I Γ to improve the credibility of microelectronic products, and this electrical property and reliability are improved by patterning the conductor-containing layer - copper 12 hydrogen The result of treatment with plasma and an argon-containing plasma. EXAMPLES: One person manufactures a microelectronic product according to a preferred embodiment of the present invention, and simultaneously applies a "containing yttrium plasma and an argon-containing plasma to pattern the first steel 12 containing the conductor layer: and the hydrogen-containing plasma is processed. The processing conditions are: (1) the pressure in the reaction chamber is about β mtorr (Tower), (2) the energy of the radio wave source is about (9) watts, and the bias voltage is about 100 watts; (3) the temperature of a substrate is about Celsius 2 〇〇 degree; (sentence hydrogen flow rate is about _ standard cubic centimeters per minute (standard cubic 匸 her axis (10) Per 黯 *, SCCM); and (7) processing time is about cutting and argon plasma processing conditions are ... 1) The pressure in the reaction chamber is about 50 mt〇IT (Tayl); (2) The energy of the radio wave source is about 700 watts, and the bias energy is about 1 watt; (3) The temperature of the substrate is about 200 degrees Celsius; (4) argon flow rate is about 1 〇SCCM; and (5) treatment time is 1, 4, 10 and 14 seconds. For the purpose of comparison, the stomach uses an additional microelectronic product to make it The first copper containing the 'body layer patterning is treated only by the hydrogen-containing plasma, and the patterned layer containing the conductor layer is no longer treated by an argon-containing plasma. A copper. Using a conventional technique to calculate the resistance in series with a microelectronic product, the result of the calculation is shown in Fig. 7. In Fig. 7, the data point indicated by reference numeral 7〇 is representative, micro The conductor-containing patterned first copper in the electronic product is treated via both a hydrogen-containing plasma and an argon-containing plasma. The data points indicated by reference numeral 72 are representative, and the conductors in the microelectronic product 15 1281216 β The first layer of copper is patterned by the fascinating layer, which has only been treated with hydrogen-containing plasma. The comparison results shown in Figure 7 of the Human-Matrix can be obtained through the treatment of both hydrogen-containing plasma and plasma. The conductor layer patterning the first copper has a lower and more uniform contact resistance than patterning the first copper via the conductor layer containing the milk-containing plasma. The error is detected by the conductor layer pattern formed according to the present invention. The atomic round spectrum of Γ θ above the copper to further detect high contact resistance

2 sources. The patterned copper layer containing the conductor layer is not: (1) after deposition, (2) treatment with only hydrogen electro-ice, or (3) treatment with only argon-containing plasma. The spectrum of the original radiation shown is shown in Figure 8. In Fig. 8, the curve indicated by reference numeral 8 is representative, and the curve containing the conductor layer patterned copper is not represented by any of the electrodes 82, and the patterned layer containing copper is only included. Hydrogen plasma treatment. The curve indicated by reference numeral 84 is that the patterned copper of the conductor layer is treated only by the argon-containing plasma. All of the songs ^ showed a corresponding carbon absorption spectrum at 275 ev. However, 曲线, with reference to the curve indicated by numeral 82, has an additional absorption spectrum 83 at an energy of 278 ev. This additional absorption spectral tip is believed to be caused by the bond between the group and the carbon. Thus, although the present invention is not intended to be associated with any operational theorem, however, the patterned layer containing copper is treated by a hydrogen-containing plasma such that the patterned layer-containing copper has a hydrogenated surface, and the hydrogenated surface can be Gas-containing (or I-gas) plasma is removed. If not removed, the hydrogenated surface will hinder the formation of the conductor layer, especially when the original 16

The I281216 sublayer deposition chemical vapor deposition method uses metals and carbonaceous materials as source materials. According to the above description, the scope of the present invention is not only for forming a nitride button barrier layer on the conductor-containing layer copper, but the present invention is more applicable to the treatment of any conductor base layer formed into an oxide or other residue. The oxide or residue can be removed by a hydrogen-containing plasma. The present invention can also be used to form a second conductor layer, such as a conductor barrier layer, by using a metal and a carbonaceous material as a source material on the copper containing the conductor layer. Although the present invention has been described above in terms of a preferred embodiment, it is not intended to limit the invention, and various modifications and changes may be made without departing from the spirit and scope of the invention. Therefore, the scope of the present invention is defined by the scope of the appended claims. BRIEF DESCRIPTION OF THE DRAWINGS In order to make the above and other objects (five), features, advantages and embodiments of the present invention more apparent, the detailed description of the drawings is as follows: Figure 1 to Figure 6 show a series of A schematic cross-sectional view of each stage of the fabrication of a microelectronic product in accordance with a preferred embodiment of the present invention. Fig. 7 is a graph showing the relationship between the cumulative probability and the contact resistance when the microelectronic product is manufactured according to the method of the present invention and the method according to the invention. Figure 8 is a diagram showing the atomic radiation spectrum of a tantalum nitride layer according to the method of the present invention and the method according to the invention. 17 95, ίΐ. 3 0

1281216 [Description of main component symbols] 10 substrate 11 inlaid hole 12 containing conductor layer pattern copper 12' hydrogen-containing plasma treated conductor layer containing patterned copper 12'' containing hydrogen and argon-containing plasma treated conductor layer Copper 14a and 14b patterned first barrier layers 16a and 16b patterned first dielectric layers 18a and 18b patterned etch stop layers 20a and 20b patterned second dielectric layers 22a and 22b patterned flat stop Layer 24 side spacer layer 26 hydrogen-containing plasma 28 argon-containing plasma 30 blanket-like barrier layer 30a barrier layer 32 blanket-like conductor layer second copper 32a with conductor layer patterned second copper 18

Claims (1)

1281216 X. Patent Application Range 1. A method for manufacturing a microelectronic product, comprising: providing a substrate, wherein the substrate has an oxidized first conductor layer; treating the first conductor layer with a reducing plasma for Forming a first conductor layer after the plasma treatment; and treating the first conductor sound after the reduction plasma treatment with a pure gas plasma to form a fully processed first conductor layer. 2. The method of claim 1, further comprising forming a second conductor layer on the fully processed first conductor layer. The method of claim 2, wherein the second conductor layer is formed by a vapor deposition method using a metal and a carbonaceous material as a source material. 4. The method of claim 3, wherein the bismuth conductor layer having the sigma-electricity characteristic is formed by first using a reducing plasma and then using a blunt gas plasma instead of only 甩A reduced plasma. 5. The method of claim 1, wherein the reducing plasma is a hydrogen-containing plasma. 6. The method of claim 1, wherein the one of the group of the blunt gas 19 1281216 is selected from the group consisting of ruthenium, osmium, argon, krypton and xenon plasma, 0, 7. Apply for a patent range! The method of item i, wherein the pure gas plasma is an argon-containing plasma. = (2) The method described in the special rhyme article, wherein the pure milk power is provided and the conditions are: no, line wave source energy 600 to 800 watts, 100 watts; bias energy 10 to pure gas flow rate mo Standard cubic centimeters per minute; and reaction chamber pressures from approximately 1 to 100 milli-tons. 9. A method of manufacturing a microelectronic product, comprising: at least: a plate having a conductor layer copper on the substrate; and treating the conductor layer containing copper with a cerium-containing plasma treatment; „ Forming a 3 gas-electric two-processed process comprising forming a fully processed conductor-containing layer steel, further comprising the method described in claim 9 of the patent application, wherein the lh patent is applied for In the scope of the tenth item, the 20 1281216 conductor layer is formed by a vapor deposition method using a metal and a carbonaceous material as a source material. The method of claim 11, wherein the method is formed. The second conductor layer for improving electrical properties first utilizes a hydrogen-containing plasma, and then uses an argon-containing plasma instead of using only one hydrogen-containing plasma. φ 13 · as described in claim 9 The method, wherein the gas-containing plasma is selected from the group consisting of hydrogen plasma and ammonia plasma. The method of claim 9, wherein the condition of providing the argon plasma is : X Radio Wave Source Energy 600 to 800 watts, a biasing energy ι〇 to 100 watts; an blunt gas flow rate of ! to 20 standard cubic centimeters per minute; and a φ reaction chamber pressure of about 1 to 100 millitorns. \ 15· A microelectronic product , comprising at least: - a substrate having an oxidized first-conductor layer thereon, wherein the first-conductor layer has been used first - reducing money, and then using - blunt gas electropolymerization. The microelectronic product of claim 15 further comprising a second conductor layer formed on the first conductor layer. 21 1281216. The microelectronic product according to claim 16, wherein the conductor layer A microelectronic product according to claim 15 wherein the reduced plasma is a hydrogen-containing plasma. The microelectronic product of claim 15 is obtained by a vapor deposition method using a metal and a carbonaceous material. </ RTI> </ RTI> </ RTI> <RTIgt; </ RTI> <RTIgt; </ RTI> <RTIgt; </ RTI> <RTIgt; </ RTI> <RTIgt; </ RTI> <RTIgt; The conditions of the plasma are: radio Wave frequency energy source 600 to 800 W, a bias power to 100 watts 1〇; noble gas flow rate of 1 to 20 standard cubic centimeter per minute; and a chamber pressure of about 1 torr to 22 milli 1〇〇.