SEMICONDUCTOR APPARATUS AND FORMING METHOD FOR FERROELECTRIC THIN FILM
20240154035 ยท 2024-05-09
Inventors
Cpc classification
H01L21/31
ELECTRICITY
H01L29/40111
ELECTRICITY
H01L29/04
ELECTRICITY
H01L29/78391
ELECTRICITY
H01L29/66083
ELECTRICITY
International classification
H01L21/28
ELECTRICITY
Abstract
A semiconductor apparatus includes an Si substrate and a ferroelectric thin film. The ferroelectric thin film is formed on the Si substrate. The ferroelectric thin film includes HfN.sub.x (1<x) having a rhombohedral crystal structure.
Claims
1. A semiconductor apparatus comprising: a Si substrate; and a ferroelectric thin film formed on the Si substrate and including HfN.sub.x (1<x) having a rhombohedral crystal structure.
2. The semiconductor apparatus according to claim 1, wherein 1.1?x?1.3 holds true.
3. The semiconductor apparatus according to claim 1, wherein 1.15?x?1.2 holds true.
4. The semiconductor apparatus according to claim 1, further comprising an SiO.sub.2 layer formed outside an active region in which the semiconductor device is formed.
5. The semiconductor apparatus according to claim 1, comprising: a contact layer including HfN.sub.y (y<1) formed on the ferroelectric thin film; and a metal electrode formed on the contact layer.
6. The semiconductor apparatus according to claim 1, wherein the ferroelectric thin film has a thickness of 3 nm to 20 nm.
7. A forming method for a ferroelectric thin film, comprising: forming a HfN.sub.x (1<x) layer by depositing Hf on a Si substrate using an Electron Cyclotron Resonance (ECR) sputtering method in a gas atmosphere including N.sub.2 and Ar; crystalizing the HfN.sub.x layer into a rhombohedral crystal structure by subjecting it to heat treatment after it is formed.
8. A semiconductor apparatus comprising a transistor, wherein the transistor comprises: a Si substrate; a ferroelectric thin film formed in a gate region on the Si substrate, and including HfN.sub.x (1<x) having a rhombohedral crystal structure; and n.sup.+ layers formed in a drain region and a source region each adjacent to the gate region on the Si substrate.
9. The semiconductor apparatus according to claim 8, wherein 1.1?x?1.3 holds true.
10. The semiconductor apparatus according to claim 8, wherein 1.15?x?1.2 holds true.
11. The semiconductor apparatus according to claim 8, further comprising a SiO.sub.2 layer formed on the Si substrate such that it is formed outside an active region including the gate region, the source region, and the drain region.
Description
BRIEF DESCRIPTION OF THE DRAWINGS
[0024] Embodiments will now be described, by way of example only, with reference to the accompanying drawings which are meant to be exemplary, not limiting, and wherein like elements are numbered alike in several Figures, in which:
[0025]
[0026]
[0027]
[0028]
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[0030]
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[0036]
DETAILED DESCRIPTION
Outline of Embodiments
[0037] Description will be made regarding the outline of several exemplary embodiments of the present disclosure. The outline is a simplified explanation regarding several concepts of one or multiple embodiments as a preface to the detailed description described later in order to provide a basic understanding of the embodiments. That is to say, the outline described below is by no means intended to restrict the scope of the present invention and the present disclosure. Furthermore, the outline described below is by no means a comprehensive outline of all possible embodiments. That is to say, the outline is by no means intended to identify the indispensable elements of the embodiments. For convenience, in some cases, an embodiment as used in the present specification represents a single or multiple embodiments (examples and modifications) disclosed in the present specification.
[0038] The outline is not meant to be an extensive outline of all conceivable embodiments. Furthermore, the outline is not intended to identify essential elements of all the embodiments or specific essential elements, nor to define the scope of part of or all the embodiments. The sole purpose of the outline is to propose several concepts of one or multiple embodiments in a simplified form as a prelude to the more detailed description that is presented later.
[0039] Conventionally, there has been research on hafnium nitride (HfN) directing attention to its characteristics as a high-k insulating material. However, such research has mainly been conducted for amorphous HfN (Non-patent document 4).
[0040] Also, Non-patent document 5 reports that HfN.sub.x has a different crystal structure according to the composition ratio x of N with respect to Hf Specifically, Non-patent document 5 reports that HfN.sub.1.165 has a rhombohedral crystal structure. However, there has been no report that HfN exhibits ferroelectricity.
[0041] The present inventor has focused on the asymmetric structure of the rhombohedral crystal system of HfN.sub.x. The present inventor has acquired the idea that such an asymmetric structure has the potential to provide a HfN.sub.x thin film having ferroelectricity.
[0042] A semiconductor apparatus according to one embodiment includes a Si substrate and a ferroelectric thin film formed on the Si substrate and including HfN.sub.x (1<x) having a rhombohedral crystal structure.
[0043] With such an arrangement in which the ratio x of N in HfN.sub.x is larger than 1, this is capable of providing the crystal structure of HfN.sub.x with asymmetry, thereby enabling the provision of ferroelectricity. The manufacturing process of the semiconductor apparatus requires no oxygen (O), which is required for the formation of HfO.sub.2. Instead, N is used. Accordingly, no SiO.sub.2 layer is formed as an interface between the ferroelectric thin film and the Si substrate. Furthermore, the nitridation rate of Si is small as compared with the oxidation rate thereof. Moreover, the energy required for a reaction is larger with N than with O. Accordingly, even in a case in which the semiconductor apparatus is subjected to heat treatment, a SiN layer having a low dielectric constant does not readily occur as an interface between HfN.sub.x and Si, thereby providing a high-quality ferroelectric thin film.
[0044] With this, as x becomes closer to 1, the HfN.sub.x readily becomes a metallic crystal structure. In contrast, as x becomes closer to 1.33, the HfN.sub.x readily becomes an insulating stable-phase crystal structure. Therefore, in one embodiment, an arrangement may be made in which 1.1?x?1.3 holds true. More preferably, an arrangement may be made in which 1.15?x?1.2 holds true.
[0045] In one embodiment, the semiconductor apparatus may further include an SiO.sub.2 layer formed outside an active region in which the semiconductor device is formed. With such an arrangement including the SiO.sub.2 layer, this is capable of suppressing the occurrence of leakage from a side face of the device, thereby providing improved device characteristics.
[0046] In one embodiment, the semiconductor apparatus may include: a contact layer including HfN.sub.y (y<1) formed on the ferroelectric thin film; and a metal electrode formed on the contact layer. In this example, as y becomes closer to 0, the HfN.sub.y is readily oxidized. In contrast, as y becomes closer to 1, the resistance of the HfN.sub.y becomes higher. Accordingly, y is preferably designed to be 0.3?y?0.8.
[0047] In one embodiment, the ferroelectric thin film may have a thickness of 3 nm to 20 nm.
[0048] A forming method for a ferroelectric thin film according to one embodiment includes: forming a HfN.sub.x (1<x) layer by depositing Hf on a Si substrate using an Electron Cyclotron Resonance (ECR) sputtering method in a gas atmosphere including N.sub.2 and Ar; crystalizing the HfN.sub.x layer into a rhombohedral crystal structure by subjecting it to heat treatment after it is formed.
[0049] A semiconductor apparatus according to one embodiment includes a transistor. The transistor includes: a Si substrate; a ferroelectric thin film formed in a gate region on the Si substrate, and including HfN.sub.x (1<x) having a rhombohedral crystal structure; and n.sup.+ layers formed in a drain region and a source region each adjacent to the gate region on the Si substrate.
[0050] With such an arrangement in which the ratio x of N in HfN.sub.x is larger than 1, this is capable of providing the crystal structure of HfN.sub.x with asymmetry, thereby enabling the provision of ferroelectricity. With such an arrangement in which the insulating layer of HfN.sub.x is used as a gate insulating film, this prevents the formation of a layer having a low dielectric constant between the gate insulating film and the Si substrate. This provides a high-performance ferroelectric gate transistor (MFSFET: Metal-Ferroelectric-Semiconductor Field-Effect Transistor). In a case in which such a MFSFET is employed as a memory storage element, this reduces the effect of a depolarizing electric field as compared with the MFSFET employing an HfO.sub.2 ferroelectric thin film as a gate insulating film, thereby providing improved memory characteristics.
[0051] In one embodiment, an arrangement may be made in which 1.1?x?1.3 holds true. More preferably, an arrangement may be made in which 1.15?x?1.2 holds true.
[0052] In one embodiment, the semiconductor apparatus may further include a SiO.sub.2 layer formed on the Si substrate such that it is formed outside an active region including the gate region, the source region, and the drain region. This is capable of suppressing the occurrence of leakage from a side face of the device, thereby providing improved device characteristics.
Embodiments
[0053] Description will be made below regarding the preferred embodiments with reference to the drawings. The same or similar components, members, and processes are denoted by the same reference numerals, and redundant description thereof will be omitted as appropriate. The embodiments have been described for exemplary purposes only, and are by no means intended to restrict the present disclosure or the present invention. Also, it is not necessarily essential for the present invention that all the features or a combination thereof be provided as described in the embodiments.
[0054] In the present specification, the state represented by the phrase the member A is coupled to the member B includes a state in which the member A is indirectly coupled to the member B via another member that does not substantially affect the electric connection between them, or that does not damage the functions or effects of the connection between them, in addition to a state in which they are physically and directly coupled.
[0055] Similarly, the state represented by the phrase the member C is provided between the member A and the member B includes a state in which the member A is indirectly coupled to the member C, or the member B is indirectly coupled to the member C via another member that does not substantially affect the electric connection between them, or that does not damage the functions or effects of the connection between them, in addition to a state in which they are directly coupled.
[0056] It should be noted that the scale of the components shown in the drawings is expanded or reduced as appropriate for ease of understanding.
[0057]
[0058] The ferroelectric thin film 120 is formed on the Si substrate 110 and includes HfN.sub.x (1<x). The composition ratio x is in a range of 1.1?x?1.3. Preferably, the composition ratio x is in a range of 1.15?x?1.2. Furthermore, the ferroelectric thin film 120 may be designed to have a thickness of 3 nm to 20 nm. For example, the ferroelectric thin film 120 may be designed to have a thickness of 10 nm.
[0059]
[0060] The above is the basic configuration of the semiconductor apparatus 100. The multilayer structure of the Si substrate 110 and the ferroelectric thin film 120 is a ferroelectric material/semiconductor multilayer structure. Furthermore, if a metal electrode is formed on the ferroelectric material/semiconductor multilayer structure, it becomes a MFS structure. It can be clearly understood by those skilled in this art that various kinds of semiconductor apparatuses such as diodes, transistors, etc., can be formed based on the basic structure shown in
[0061]
[0062] The contact layer 130 includes HfN.sub.y (y<1) and is formed on the ferroelectric thin film 120. The metal electrode 140 is formed of a metal material such as Al or the like and is formed on the contact layer 130. In addition to Al, examples of materials that can be employed as the metal electrode 140 include polycrystalline Si, TiN, W, Pt, etc. The thickness of the ferroelectric thin film 120 may be designed to be 3 nm to 20 nm, e.g., to be 10 nm. Furthermore, the thickness of the contact layer may be designed to be 10 nm to 30 nm, e.g., to be 20 nm.
[0063] A MFS diode can be formed by additionally forming an electrode on the Si substrate 110 side of the MFS structure. Furthermore, by forming a drain and a source in the Si substrate 110, this allows a transistor to be formed with the metal electrode 140 as a gate.
[0064]
[0065] Next, description will be made regarding a manufacturing method for the ferroelectric thin film 120 and a manufacturing method for the semiconductor apparatus 100.
[0066] Subsequently, as shown in
[0067] Subsequently, as shown in
[0068] The ferroelectric thin film 120 and the contact layer 130 shown in
[0069] Subsequently, as shown in
[0070] Subsequently, as shown in
[0071] The above is an example of the manufacturing method for the semiconductor apparatus 100B. It can be clearly understood by those skilled in this art that modifications may be made for each process, and that the order of several processes may be interchanged. With the manufacturing method using an in-situ process, by switching the atmosphere gas, this is capable of forming a multilayer structure of the ferroelectric thin film 120 and the contact layer 130. Accordingly, this manufacturing method is advantageous from the viewpoint of the manufacturing cost and the manufacturing time.
[0072] Next, description will be made regarding a sample (which will also be referred to as a diode sample) of an actually manufactured semiconductor apparatus 100B and evaluation thereof.
[0073] The size of each layer of the diode sample thus manufactured is as follows. [0074] Ferroelectric thin film 120: 10 nm [0075] Contact layer 130: 20 nm
[0076] Furthermore, the upper electrode 140 is designed to be 50?50 ?m.sup.2.
[0077] Description will be made below regarding the formation conditions for each layer.
[0078] The substrate cleaning shown in
[0079] The ferroelectric thin film 120 and the contact layer 130 shown in
[0080] The heat treatment shown in
[0081]
[0082] Description will be made below regarding the evaluation results of a diode sample manufactured under the conditions described above.
[0083]
[0084] It can be understood that all the samples were formed in a mixed form of both the c-Hf.sub.3N.sub.4(200) crystal structure and the c-HfN.sub.x (111) crystal structure. However, it can be understood that, in a case in which the sample is formed in a condition of 400? C./5 minutes, the ?-HfN.sub.x (111) crystal structure is a dominant component, and such a sample has a rhombohedral crystal structure.
[0085] That is to say, it can be understood that, from among the deposition conditions for the samples that were measured in this measurement, the sample formed by heat treatment in a condition of 400? C./5 minutes can effectively provide a rhombohedral crystal structure. Description will be made regarding the evaluation results of the electrical characteristics and magnetic characteristics of a HfN.sub.1.15 thin film sample (which will be referred to as a MFS diode sample hereafter) manufactured in the conditions described above.
[0086]
[0087] Furthermore, anti-voltage 2V.sub.C, i.e., the voltage hysteresis width, was 7.6 V, and the residual polarization 2P.sub.r was 24.0 ?C/cm.sup.2. This is dramatically larger than the conventionally reported residual polarization 2P.sub.r of HfO.sub.2 of 2.5 ?C/cm.sup.2 with no other elements added (Non-patent document 6). One of the reasons why such a large residual polarization is provided is that the displacement of nitrogen (N) atoms due to the electric field is larger than that of oxygen atoms.
[0088]
[0089]
[0090]
[0091] With such an arrangement provided with the SiO.sub.2 layer 160, this is capable of reducing leakage from the side face of the ferroelectric thin film 120 of the diode to the Si substrate 110, thereby allowing the characteristics to be further improved.
[0092]
[0093] The transistor 200 is formed on the Si substrate 110. The ferroelectric thin film 120 is configured as a gate insulating film formed in the gate region of the Si substrate 110. The ferroelectric thin film 120 includes HfN.sub.x (1<x) having a rhombohedral crystal structure.
[0094] In the present embodiment, the SiO.sub.2 layer 160 is formed on the Si substrate 110 such that it surrounds the active region 202 including the drain (D), gate (G), and source (S).
[0095] The n.sup.+ layers 112 and 114 are formed in the source region and the drain region of the Si substrate 110, respectively. The contact layer 130 is formed on the ferroelectric thin film 120. However, the boundary between the ferroelectric thin film 120 and the contact layer 130 is not shown in
[0096] In the gate region (G), the metal electrode 140, which is configured as the gate electrode, is formed on the ferroelectric thin film 120 (contact layer 130). Furthermore, a source electrode 170 and a drain electrode 172 are formed such that they are drawn from the n.sup.+ layers 112 and 114.
[0097] The above is the configuration of the semiconductor apparatus 100D. It should be noted that, in a case in which the MFS transistor 200 is formed as shown in
Usage
[0098] The MFS device described above may be employed as a nonvolatile memory cell using the change in capacitance or the change in the threshold voltage.
[0099] The usage of the MFS device is not restricted to such nonvolatile memory (digital storage element). Also, the MFS device can be employed as an analog storage element using the continuous change in capacitance or threshold value according to the gate voltage. Also, the MFS device can be employed as a D/A converter. Also, such a floating gate device may be employed as a neural calculation element employed in a neural network. It can be anticipated that such a MFS device can be applied to neurodevices and the like that emulate the human brain, which provide weighted calculation of input signals.
[0100] The above-described embodiments show only an aspect of the mechanisms and applications of the present invention. Rather, various modifications and various changes in the layout can be made without departing from the spirit and scope of the present invention defined in appended claims.
[0101] Description has been made regarding the present invention with reference to the embodiments using specific terms. However, the above-described embodiments show only an aspect of the mechanisms and applications of the present invention. Rather, various modifications and various changes in the layout can be made without departing from the spirit and scope of the present invention defined in appended claims.