The present disclosure relates to methods for manufacturing semiconductor devices, and in particular relates to methods for manufacturing semiconductor devices which provide improved electrical characteristics for dielectric films.
With higher integration density and larger storage capacity, gate insulation films of semiconductor devices are being manufactured thinner in thickness. Moreover, silicon oxide (SiO2) films are typically used as gate insulation films because of their beneficial properties with respect to thermal stability, reliability and are also convenient to manufacture. However, as silicon oxide films have a dielectric constant of about 3.9 which is not considered to be a relatively high dielectric constant, these silicon oxide films typically need to be scaled down in thickness. There is a limit, however, to how much a silicon oxide film may be physically scaled down in thickness due to the possibility of a steep increase in the amount of leakage current.
Accordingly, high-dielectric films suitable for use as gate insulation films which may replace such conventional silicon oxide films are being investigated. If such high-dielectric films are used as a gate insulation film, it is permissible to form them with a larger thickness than the thicknesses of he conventional silicon oxide films under the same capacitance, thereby reducing the amount of leakage current therein. There are various materials which may be used as high-dielectric films, such as, for example, (BaX, Sr1−X)TiO3(e.g. barium strontium titanate (BST), titanium oxide (tiO2), tantalum oxide (Ta2O5), aluminum oxide (Al2O3), zirconium oxide (ZrO2), Zr silicate, hafnium oxide (HfO2), or Hf silicate.
However, there may still be difficulties associated with using such high-electric films as the gate insulation film. For example, when a film of BST, TiO2, or TaO2 is directly deposited on a silicon substrate, the interface characteristics with the substrate may worsen to thereby increase the amount of leakage current therethrough. Moreover, as a result, the interface trap charge density may also increase to thereby significantly lower the mobility of carriers. Furthermore, using a high-dielectric film by itself may make it difficult to stabilize the threshold voltage of a field effect transistor. Thus, there is a need for a method for manufacturing semiconductor devices which provides improved electrical characteristics for dielectric films.
Exemplary embodiments of the present invention provide a method of manufacturing a semiconductor device which provides improved electrical characteristics for a dielectric film.
In accordance with an exemplary embodiment of the present invention, a method of manufacturing a semiconductor device is provided. This method includes depositing a high-dielectric film on a semiconductor substrate and performing an oxygen plasma treatment on the high-dielectric film deposited on the semiconductor substrate. The method further includes forming an electrode on the oxygen plasma treated high-dielectric film.
In an exemplary embodiment, the semiconductor substrate may be formed of a material comprising silicon (Si), germanium (Ge), or silicon-germanium (SiGe). The high-dielectric film may be made of a metal oxide or a metal silicate. The method may further comprise forming an interface layer on the semiconductor substrate before depositing the high-electric film. The interface layer may be formed of silicon oxide or silicon oxynitride. The oxygen plasma treatment may be carried out by remote oxygen plasma treatment or direct oxygen plasma treatment. The electrode may be made of at least one material selected from the group consisting of doped polysilicon, metal, conductive metal nitride, and metal silicide. The method may further comprise forming a capping layer on the oxygen-plasma treated high-dielectric film after processing the oxygen plasma treatment. The capping layer may be formed of silicon nitride. The method may further comprise processing a supplementary oxygen plasma treatment after forming the capping layer. The method may further comprise performing a nitrification treatment to the high-dielectric film before or after processing the oxygen plasma treatment.
In accordance with an exemplary embodiment of the present invention, a method of manufacturing a semiconductor device comprises is provided. The method includes depositing a multi-level high-dielectric film including a plurality of high-dielectric layers stacked on a semiconductor substrate and performing an oxygen plasma treatment on the multi-level high-dielectric film deposited on the semiconductor substrate. The method further includes forming an electrode on the oxygen plasma treated multi-level high-dielectric film.
In an exemplary embodiment, the oxygen plasma treatment may be carried out after depositing all the plurality of high-dielectric layers of the multi-level high-dielectric film. Otherwise, the oxygen plasma treatment may be carried out after depositing each of the plurality of high-dielectric layers of the multi-level high-dielectric film.
Exemplary embodiments of the present invention can be understood in more detail from the following description taken in conjunction with the accompanying drawings, in which:
Exemplary embodiments of the present invention will be described below in more detail with reference to the accompanying drawings. The present invention may, however, be embodied in different forms and should not be constructed as limited to the exemplary embodiments set forth herein.
It will also be understood that when a layer (or film) is referred to as being ‘on’ another layer or substrate, it can be directly on the other layer or substrate, or intervening layers may also be present. Further, it will be understood that when a layer is referred to as being ‘under’ another layer, it can be directly under, and one or more intervening layers may also be present. In addition, it will also be understood that when a layer is referred to as being ‘between’ two layers, it can be the only layer between the two layers, or one or more intervening layers may also be present. Like reference numerals refer to like elements throughout.
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The oxygen plasma treatment cures the high-dielectric film 105. Thereby, the oxygen-plasma treated high-dielectric film 105a provides improved leakage current properties. Namely, the leakage current through the oxygen-plasma treated high-dielectric film 105a is reduced to the minimum degree. In forming the interface layer 102, it is significant to control processing conditions of the oxygen plasma treatment so as not to raise the thickness thereof.
Before or after conducting the oxygen plasma treatment, a nitrification treatment is performed on the semiconductor substrate 100 including the high-dielectric film 105 or 105a. This nitrification treatment may contribute to improve the thermal stability of the high-dielectric film 105. The nitrification treatment may be carried out by means of a thermal nitrification process at a temperature of about 700 to about 1000° C. or a plasma nitrification process under a temperature of less than about 500° C. The thermal nitrification process may be performed with ammonia (NH3) gas at a temperature of about 700 to about 1000° C. under a pressure of about 1 to about 100 Torr for about 30 seconds through about 2 minutes. The plasma nitrification process may be performed at a temperature less then about 500° C. under a pressure of about 5 to about 100 m Torr for about 30 seconds through about 5 minutes.
When a gate electrode subsequently formed is made of polysilicon doped with impurities, it is preferred to conduct the nitrification treatment on the oxygen-plasma treated high-dielectric film 105a. If the nitrification treatment is carried out before the oxygen plasma treatment, it reduces the concentration of nitrogen in the oxygen-plasma treated high-dielectric film 105a and weakens bonding forces among atoms, because of disturbance in the combination between nitrogen and atoms of the high-dielectric film 105, by which impurities of the gate electrode may be diffused through the high-dielectric film 105a.
Otherwise, when the gate electrode is made of a conductive film (e.g., conductive metallic nitride such as titanium nitride or tantalum nitride) or metal (e.g., tungsten or molybdenum), except the doped polysilicon, the nitrification treatment may be carried out before or after the oxygen plasma treatment. After the nitrification treatment, a high-temperature thermal process may be conducted under a temperature of about 800 to about 1100° C. to enhance the electrical characteristics of the high-dielectric film 105 or 105a.
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This process of oxygen plasma treatment may be carried out in the same manner as the first exemplary embodiment. Namely, the oxygen plasma treatment may be conducted using, for example, a remote oxygen plasma or a direct oxygen plasma treatment. The oxygen plasma treatment may be carried out under the atmosphere with oxygen of about 1 SLM (standard liters per minute) and nitrogen of about 0.12 SLM. Gas supplying temperature is preferred to be about 25 to about 300° C. including room temperature. More preferably, it is proper to carry out this process under about 100° C. A power rate is set at about 100 to about 400W for about 40 to about 80 seconds. In forming the interface layer 202, it is significant to control processing conditions of the oxygen plasma treatment so as not to raise the thickness thereof.
Before or after conducting the oxygen plasma treatment, a nitrification treatment is performed on the high-dielectric film 205 or 205a. This nitrification treatment may contribute to improve the thermal stability of the high-dielectric film 205. The nitrification treatment may be carried out by means of a thermal nitrification process at a temperature of about 700 to about 1000° C. or a plasma nitrification process under a temperature of less than about 500° C. The thermal nitrification process may be performed with ammonia (NH3) gas at a temperature of about 700 to about 1000° C. under a pressure of about 1 to about 100 Torr for about 30 seconds through about 2 minutes. The plasma nitrification process may be performed at a temperature of less then about 500° C. under a pressure of about 5 to about 100 mTorr for about 30 seconds through about 5 minutes.
When a gate electrode subsequently formed is made of polysilicon doped with impurities, it is preferred to conduct the nitrification treatment on the oxygen-plasma treated high-dielectric film 205a. Namely, the nitrification treatment may be conducted after the oxygen plasma treatment. If the nitrification treatment is carried out before the oxygen plasma treatment, the concentration of nitrogen in the oxygen-plasma treated high-dielectric film 205a may be reduced and the bonding forces among atoms may be weakened, because of disturbance in the combination between nitrogen and atoms of metal oxide or metal silicate, by which impurities (or dopants) of the gate electrode may diffuse through the high-dielectric film 205a to thereby result in the deterioration of electrical characteristic of the high-dielectric film 205a. On the other hand, when the gate electrode is made of a conductive material containing metal, the nitrification treatment may be carried out before or after the oxygen plasma treatment.
After the nitrification treatment, a high-temperature thermal process under a temperature of about 800 to about 1100° C. may be conducted to enhance the electrical characteristics of the high-dielectric film 205 or 205a.
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An additional processing step may be conducted for forming an interface layer 302 of insulative material that is interposed between the multi-level high-dielectric film 305 and the semiconductor substrate 300, thereby enhancing the interface characteristic therebetween to increase the mobility of electrons (or holes) in a channel region. The interface layer 302 may be made of, for example, silicon oxide (SiO2) or silicon oxynitride (SiON). The interface layer 302 may be formed to a thickness of about 5 to about 20 Å.
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This process of oxygen plasma treatment may be carried out in the same manner as the first or second exemplary embodiment. In other words, the oxygen plasma treatment may be processed using, for example, remote oxygen plasma or direct oxygen plasma treatment. The oxygen plasma treatment may be carried out under the atmosphere with oxygen of about 1 SLM and nitrogen of about 0.12 SLM. Gas supplying temperature is preferred to be about 25 to about 300° C., including room temperature. For example, this process may be carried out under about 100° C. A power rate is set at about 100 to about 400W for about 40 to about 80 seconds. In forming the interface layer 302, it is significant to control processing conditions of the oxygen plasma treatment so as not to raise the thickness thereof.
The oxygen plasma treatment may include first and second steps of oxygen plasma treatment. The first oxygen plasma treatment begins after depositing the first high-dielectric layer 303, and the second oxygen plasma treatment begins after depositing the second high-dielectric layer 304. As also aforementioned, the oxygen plasma treatment may be carried out once after continuously depositing the first and second high-electric layers 303 and 304. The first and second oxygen plasma treatment steps may be carried out in the aforementioned manner of oxygen plasma treatment.
Before or after conducting the oxygen plasma treatment, a nitrification treatment for improving thermal stability of the multi-level high-dielectric film 305 and 305a may be performed. The nitrification treatment may be carried out by means of a thermal nitrification process at a temperature of about 700 to about 1000° C. or a plasma nitrification process under a temperature less than about 500° C. When a gate electrode subsequently formed is made of polysilicon doped with impurities, the nitrification treatment may be conducted after completing the oxygen plasma treatment. This is because of the reason described relevant to the first or second exemplary embodiment. The thermal nitrification process may be performed with ammonia (NH3) gas at a temperature of about 700 to about 1000° C. under a pressure of about 1 to about 100 Torr for about 30 seconds through about 2 minutes. The plasma nitrification process may be performed at a temperature less then about 500° C. under a pressure of about 5 to about 100 mTorr for about 30 seconds through about 5 minutes. After completing the nitrification treatment, a high-temperature thermal operation may be processed at a temperature of about 800 to about 1100° C. to improve the electrical characteristics of the multi-level high-dielectric film 305 or 305a.
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In addition, a further processing step of forming an interface layer 402 of insulative material that is interposed between the multi-level high-dielectric film 405 and the semiconductor substrate 400 may be conducted. The interface layer 402 functions to enhance the interface characteristic therebetween to increase the mobility of electrons (or holes) in a channel region. The interface layer 402 may be made of, for example, silicon oxide (SiO2) or silicon oxynitride (SiON) by means of various processing ways.
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This process of oxygen plasma treatment may be carried out in the same manner with the first, second, or third exemplary embodiment. In other words, the oxygen plasma treatment may be processed using remote oxygen plasma or direct oxygen plasma treatment. The oxygen plasma treatment may be carried out under the atmosphere with oxygen of about 1 SLM and nitrogen of about 0.12 SLM. Gas supplying temperature is preferred to be about 25 to about 300° C., including room temperature. More preferably, it is proper to carry out this process under about 100° C. A power rate is set at about 100 to about 400W for about 40 to about 80 seconds. In forming the interface layer 402, it is significant to control processing conditions of the oxygen plasma treatment so as not to raise the thickness thereof.
The oxygen plasma treatment may include first and second steps of oxygen plasma treatment. The first oxygen plasma treatment begins after depositing the first high-dielectric layer 403, and the second oxygen plasma treatment begins after depositing the second high-dielectric layer 404. As also aforementioned, the oxygen plasma treatment may be carried out once after continuously depositing the first and second high-electric layers 403 and 404. The first and second oxygen plasma treatment steps may be carried out in the aforementioned manner of oxygen plasma treatment.
Before or after conducting the oxygen plasma treatment, it is proper to perform a nitrification treatment for improving the thermal stability of the multi-level high-dielectric film 305 and 305a. The nitrification treatment may be carried out by means of a thermal nitrification process at a temperature of about 700 to about 1000° C. or a plasma nitrification process under a temperature less than about 500° C. When a gate electrode subsequently formed is made of polysilicon doped with impurities, it is preferred to conduct the nitrification treatment after completing the oxygen plasma treatment. This is because of the reason described relevant to the first or second exemplary embodiment. The thermal nitrification process may be performed with ammonia (NH3) gas at a temperature of about 700 to about 1000° C. under a pressure of about 1 to about 100 Torr for about 30 seconds through about 2 minutes. The plasma nitrification process may be performed at a temperature less then about 500° C. under a pressure of about 5 to about 100 mTorr for about 30 seconds through about 5 minutes. After completing the nitrification treatment, a high-temperature thermal operation may be processed at a temperature of about 800 to about 1100° to improve the electrical characteristics of the multi-level high-dielectric film 405 or 405a.
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In the aforementioned exemplary embodiments, the electrodes 120, 220, 320, and 420 are illustrated as being used for gate electrodes. But, the high-dielectric films 105a, 205a, 305a, and 405a may be used as dielectric films of capacitors, or insulation films between floating and control gates of a flash memory device. The electrodes 120, 220, 320, and 420, which are associated with the high-dielectric films 105a, 205a, 305a, and 405a used as the dielectric films of the capacitors (e.g., in DRAMs), are correspondent with top electrodes of the capacitors, and the substrates 100, 200, 300, and 400 may be correspondent with storage electrodes of the capacitors. The electrodes 120, 220, 320, and 420, which are associated with the high-dielectric films 105a, 205a, , 305a, and 405a used as the insulation films between the floating and control gates of the flash memory device, are correspondent with the control gate electrodes thereof, and the semiconductor substrates 100, 200, 300, and 400 may be correspondent with the floating gates thereof.
Accordingly, the exemplary embodiments of the invention are able to improve the electrical characteristics, e.g., a leakage current characteristic, by processing the oxygen plasma treatment on the high-dielectric film that may be employed as a gate dielectric film of a next-generation transistor. Moreover, as the characteristic of leakage current is significantly advanced by processing the oxygen plasma treatment on the composite high-dielectric film, e.g., more than dual layers, as well as on the single layer, it is possible to scale the equivalent oxide thickness.
Having described the exemplary embodiments of the present invention, it is further noted that it is readily apparent to those of reasonable skill in the art that various modifications may be made without departing from the spirit and scope of the invention which is defined by the metes and bounds of the appended claims.
Number | Date | Country | Kind |
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2005-118884 | Dec 2005 | KR | national |
This U.S. non-provisional patent application claims priority to Korean Patent Application 2005-118884 filed on Dec. 7, 2005, the disclosure of which is hereby incorporated by reference herein in its entirety.