The present invention relates to a microchip, such as a bench-top biochip and a surface potential sensor, and to an SOI substrate for the manufacture of these microchips.
In recent years, attention has been drawn to a small biochip used to efficiently analyze small amounts of sample in a short period of time. Such a microchip as described above is generally obtained by fabricating a pattern and the like having a width of several tens to several hundreds of micrometers and a depth of several to several tens of micrometers onto a substrate, such as a glass substrate, using a photolithographic technique heretofore known as semiconductor technology. This microchip is expected to be applied to fields referred to as μ-TAS (Micro-Total Analysis Systems), LOAC (Lab-On-A Chip), Bio-MEMS (Bio-Micro Electro-Mechanical Systems), Optical-MEMS, Fluidic-MEMS, and the like.
In the conventional structure of these microchips, however, there is usually provided only a portion to be figuratively referred to as a “chemical plant,” in which individual microfabricated parts intended, for example, to flow or retain a measurement sample (mostly solution) or cause a chemical reaction therein, are integrated and provided on a single chip (as the substrate of which a transparent material such as quartz is used). Hence, semiconductor elements and the like necessary for the analysis and evaluation of the measurement sample are mounted on another device separately from this microchip, thus impeding the implementation of simple, highly efficient analysis and evaluation.
In order to overcome such an impediment, there arises the need for an integrated microchip in which the “chemical plant” portion and semiconductor elements and the like necessary for the analysis and evaluation of the measurement sample are mounted on a single chip. To take a bench-top biochip as an example, a substrate transparent to incident light and a high-quality semiconductor layer for forming semiconductor elements on this transparent substrate are necessary in order to take out an electrical signal by injecting light into the measurement sample. In order to meet such needs as described above, there has been proposed using an SOS (Silicon on Sapphire) substrate which is a type of SOI substrate (see Hidekazu Uchida et al., “Characteristic, Improvement of Surface Photovoltage Method-Based Two-Dimensional Chemical Image Sensor Using SOS Substrate,” The Institute of Electrical Engineers of Japan, Chemical Sensor Workshop Material CHS-00-66 (2000) 23).
However, since an SOS substrate is obtained by heteroepitaxially growing a silicon layer on a sapphire substrate and, therefore, a high-density dislocation (lattice defect) occurs at a boundary face between silicon and sapphire due to a difference in lattice constant therebetween, it is not easy to enhance the quality of the silicon layer. In addition, there has been pointed out the problem that since the sapphire substrate itself is costly, the SOS substrate unavoidably tends to be also expensive.
Incidentally, as one of methods for obtaining an SOI substrate, there is known the SmartCut method based on the bonding together of substrates. The SmartCut method is a method in which a silicon substrate, on the bonding surface side of which hydrogen ions have been implanted, and a substrate made also of silicon or of another material are bonded together and subjected to a relatively high-temperature heat treatment. Then, a silicon thin film is thermally peeled off from a region where the concentration of the implanted hydrogen ions is highest, thus obtaining an SOI substrate (see, for example, Japanese Patent No. 3048201 and A. J. Auberton-Herve et al., “SMART CUT TECHNOLOGY: INDUSTRIAL STATUS of SOI WAFER PRODUCTION and NEW MATERIAL DEVELOPMENTS” (Electrochemical Society Proceedings Volume 99-3 (1999) pp. 93-106)).
In a case where a silicon substrate and a glass substrate are selected as substrates to be bonded together, however, the substrates are more likely to cause breakage or local cracks if the temperature of heat treatment applied to the substrates being bonded in a manufacturing process becomes higher, since the two substrates differ in thermal properties (for example, thermal expansion rate and intrinsic allowable temperature limits) from each other. From this point of view, the SmartCut method which requires high temperatures for silicon thin film separation can hardly be said preferable as a method for manufacturing an SOI substrate based on the bonding of a silicon substrate to a glass substrate.
The present invention has been accomplished in view of the above-described problems. It is therefore an object of the present invention to avoid the introduction of breakage, local cracks and the like due to a difference in thermal properties between a silicon substrate and a glass substrate, thereby providing an SOI substrate having an SOI layer superior in film uniformity, crystal quality, and electrical characteristics (carrier mobility and the like), as well as providing, using this SOI substrate, a microchip (biochip) in which a hole, a micro-flow passage or the like and a semiconductor element for analysis and evaluation are integrated into a single chip, or a macro chip, such as a surface potential sensor, capable of monitoring a change in the charge amount of a sample (for example, cell) from a detected photocurrent.
In order to solve the above-described problems, a microchip of the present invention is characterized by being fabricated using an SOI substrate manufactured by a method including steps (1) to (4) described below: (1) a step of forming a hydrogen ion-implanted layer by implanting ions into the bonding surface of a silicon substrate; (2) a step of applying a surface activation treatment to the bonding surface of at least one of the silicon substrate and the glass substrate; (3) a step of bonding together the silicon substrate and the glass substrate; and (4) a step of transferring a silicon layer onto the glass substrate by peeling off the surface layer of the silicon substrate along the hydrogen ion-implanted layer.
The step (2) of surface activation treatment can be carried out by means of at least one of plasma treatment and ozone treatment. In addition, the step (3) can include a sub-step of heat-treating the silicon substrate and the glass substrate after the bonding together, with the two substrates bonded together.
In the present invention, the sub-step of heat treatment is preferably carried out at a temperature of 100° C. or higher but not higher than 300° C. In addition, the method may include a step (step (5)) of polishing the peeling plane of the silicon layer, in succession to the step (4), so that the surface roughness (RMS) thereof is not greater than 3 nm.
The microchip of the present invention is, for example, such that one principal surface of the glass substrate has a concave portion, such as a flow passage or a hole, and a semiconductor element for analyzing/evaluating a sample attached/held to the concave portion is provided in the silicon layer provided on the other principal surface of the glass substrate.
Furthermore, the microchip of the present invention includes, for example, an insulating layer formed on a surface of the silicon layer; a sample-holding portion provided on the insulating layer; a biasing portion for forming a depletion layer in a boundary face between the insulating layer and the silicon layer; and a signal-detecting circuit for detecting the amount of photoelectric current generated depending on the thickness of the depletion layer which varies according to the amount of charge provided by an analyte held by the sample-holding portion.
An SOI substrate for the manufacture of a microchip according to the present invention is fabricated by a method including the steps (1) to (4), that is: (1) a step of forming a hydrogen ion-implanted layer by implanting ions into the bonding surface of a silicon substrate; (2) a step of applying a surface activation treatment to the bonding surface of at least one of the silicon substrate and the glass substrate; (3) a step of bonding together the silicon substrate and the glass substrate; and (4) a step of transferring a silicon layer onto the glass substrate by peeling off the surface layer of the silicon substrate along the hydrogen ion-implanted layer. Note that it is preferable that the above-described glass substrate is a quartz substrate.
Since the present invention has made it possible to fabricate an SOI substrate without applying such high-temperature treatments (for example, approximately 1000° C.) as applied in conventional methods, breakage, local cracks and the like due to a difference in thermal properties between the silicon substrate and the glass substrate are avoided. As a result, it is possible to provide an SOI substrate having an SOI layer superior in film uniformity, crystal quality, and electrical characteristics (carrier mobility and the like).
Then, a concave portion, such as a hole, a micro-flow passage or a micromixer is formed on a surface of the glass substrate of the SOI substrate thus obtained and a surface treatment is performed using a silane coupling agent or the like, so that processes required for a DNA chip or a microfluidic chip are applied. In addition, a semiconductor element portion for the analysis/evaluation of a sample attached/held to this concave portion is formed in the SOI layer. Consequently, it is possible to obtain a microchip (biochip) in which a hole, a micro-flow passage or the like and a semiconductor element for analysis/evaluation are integrated into a single chip.
Furthermore, an insulating layer, such as a silicon dioxide film or a silicon nitride film, is formed on a surface of the SOI layer, a sample-holding portion to which a measurement sample is attached or held is provided on this insulating layer, and biasing electrodes used to form a depletion layer in a boundary face between the insulating layer and the SOI layer and a signal-detecting circuit for detecting the amount of photoelectric current generated depending on the thickness of the depletion layer which varies according to the amount of charge provided by an analyte held by the sample-holding portion are further provided. Consequently, it is possible to obtain a macro chip, such as a surface potential sensor, capable of monitoring a change in the charge amount of a sample (for example, cell) from a detected photocurrent.
Hereinafter, the best mode for carrying out the present invention will be described with reference to the accompanying drawings. Note that in the following description, a glass substrate is assumed to be a quartz substrate.
[Substrate for the Manufacture of Microchips]:
Note that the diameters of these substrates are substantially the same. For the sake of convenience in a subsequent device formation process, it is advantageous to provide the same orientation flat (OF) as the OF provided in the single-crystal Si substrate 10 also in the quartz substrate 20, and bond the substrates together by aligning these OFs with each other.
First, hydrogen ions are implanted into a surface of the single-crystal Si substrate 10 (
The depth of the ion-implanted layer 11 from the surface of the single-crystal Si substrate 10 (average ion implantation depth L) is controlled by an acceleration voltage at the time of ion implantation and is determined depending on how thick an SOI layer to be peeled off is desired. For example, the average ion implantation depth L is set to approximately 2 to 3 μm and the acceleration voltage is set to 50 to 100 keV. Note that an insulating film, such as an oxide film, may be previously formed on the ion-implanted surface of the single-crystal Si substrate 10 and ion implantation may be applied through this insulating film in a process of ion implantation into Si crystal, as is commonly practiced to suppress the channeling of implanted ions.
A plasma treatment or an ozone treatment for the purpose of surface cleaning, surface activation and the like is applied to the respective bonding surfaces of the single-crystal Si substrate 10 in which the ion-implanted layer 11 has been formed and the quartz substrate 20 (
When carrying out this surface treatment by means of plasma treatment, a surface-cleaned single-crystal Si substrate to which RCA cleaning or the like has been applied previously and/or a quartz substrate is mounted on a sample stage within a vacuum chamber, and a gas for plasma is introduced into the vacuum chamber so that a predetermined degree of vacuum is reached. Note that examples of gas species for plasma used here include an oxygen gas, a hydrogen gas, an argon gas, a mixed gas thereof, or a mixed gas of oxygen and helium for use in the surface treatment of the single-crystal Si substrate. The gas for plasma can be changed as appropriate according to the surface condition of the single-crystal Si substrate or the purpose of use thereof.
If the surface treatment is performed also for the purpose of oxidizing a single-crystal Si surface, a gas containing at least an oxygen gas is used as the gas for plasma. Note that the surface of the quartz substrate is in an oxidized state and, therefore, there are no particular restrictions on such selection of a type of gas for plasma as described above. High-frequency plasma having an electrical power of approximately 100 W is generated after the introduction of the gas for plasma, thereby applying a treatment for approximately 5 to 10 seconds to a surface of the single-crystal Si substrate and/or a surface of the quartz substrate to be plasma-treated, and then finishing the treatment.
When the surface treatment is carried out by means of ozone treatment, a surface-cleaned single-crystal Si substrate to which RCA cleaning or the like has been applied previously and/or a quartz substrate is mounted on a sample stage within a chamber placed in an oxygen-containing atmosphere. Then, after introducing a gas for plasma, such as a nitrogen gas or an argon gas, into the chamber, high-frequency plasma having a predetermined electrical power is generated to convert oxygen in the atmosphere into ozone by the plasma. Thus, a surface treatment is applied for a predetermined length of time to a surface of the single-crystal Si substrate and/or a surface of the quartz substrate to be treated.
The single-crystal Si substrate 10 and the quartz substrate 20, to which such a surface treatment as described above has been applied, are bonded together with the surfaces thereof closely adhered to each other as bonding surfaces (
The bonding process temperature at this time is set to 350° C. or lower and, preferably, within a range from 100 to 300° C., taking into consideration the condition that the substrates to be used for bonding are a silicon substrate and a quartz substrate (glass substrate). The reason for selecting such a temperature as described above is because consideration is given to a difference in thermal expansion coefficient between single-crystal Si and quartz, an amount of strain due to this difference, and a relationship between the amount of strain and the thicknesses of the single crystal Si substrate 10 and the quartz substrate 20. If the thicknesses of the single-crystal Si substrate 10 and the quartz substrate 20 are almost the same with each other, thermal strain-induced cracks or separation at a bonding plane occurs due to a difference in rigidity between the two substrates when the substrates are subjected to a heat treatment at a temperature higher than 350° C., since there is a significant difference between the thermal expansion coefficient (2.33×10−6) of single-crystal Si and the thermal expansion coefficient (0.6×10−6) of quartz. In an extreme case, the breakage of the single-crystal Si substrate or the quartz substrate occurs. Accordingly, the upper limit of the heat treatment temperature is specified as 350° C. and a heat treatment is preferably applied within a temperature range of 100 to 300° C.
If a force of impact is applied to the bonded substrate using a certain technique in succession to such a treatment as described above (FIG. 1(F)), a silicon thin film peels off from the bulk portion 13 of single-crystal silicon along the hydrogen ion-implanted layer 11 due to this impact, thereby obtaining an SOI substrate having an SOI layer 12 on the quartz substrate 20 (
Note here that there can be various ways of externally applying impact in order to peel off the silicon thin film.
In
When the temperature of the heating plate 32 is kept at 300° C. or lower (for example, 250 to 300° C.) and the rear surface of the single-crystal Si substrate 10 bonded to the quartz substrate 20 is closely adhered on this heating plate 32, the single-crystal Si substrate 10 is heated by thermal conduction, thereby generating a temperature difference between the Si substrate and the quartz substrate 20. As described above, since the thermal expansion coefficient of the silicon substrate is larger than the thermal expansion coefficient of the quartz substrate, a large stress is generated between the two substrates due to the rapid expansion of the single-crystal Si substrate 10 if the single-crystal Si substrate 10 in a bonded state is heated from the rear surface thereof. The separation of a silicon thin film is caused by this stress.
The example illustrated in
Yet alternatively, as illustrated in
Evaluation of the surface condition of an SOI substrate obtained by following such a series of processes as described above showed that there were no defects, such as the local separation of a silicon thin film, traces of separation and untransferred regions. Thus, the substrate surface exhibited an extremely planar state. Measurement of a 10 μm×10 μm area of the surface of the SOI layer after separation using an atomic force microscope (AFM) showed that the RMS mean value was as excellent as no greater than 5 nm. In addition, the film-thickness variation (PV: peak-to-valley) of the SOI layer within the substrate surface was no larger than 4 nm.
Note that there may be provided a step of polishing the surface of the SOI layer 12 in succession to the step of
As described above, only low-temperature treatments are applied consistently at 350° C. or lower (preferably 300° C. or lower) in a manufacturing process of the SOI substrate of the present invention. Whereas a conventional “bonding method” requires high-temperature heat treatments for the purpose of obtaining sufficient bonding strength or breaking silicon atomic bonds (see, for example, Japanese Patent No. 3048201 and Japanese Patent Laid-Open No. 11-145438), the present invention does not require such high-temperature heat treatments (for example, 1000° C. or higher). The SOI substrate therefore has an SOI layer having little defects and superior in film uniformity, crystal quality, and electrical characteristics (carrier mobility and the like). Furthermore, according to the above-described process, it is possible to obtain the SOI substrate without causing any breakage, cracks and the like due to a difference in thermal expansion coefficient between the silicon substrate and the quartz substrate since the SOI substrate does not undergo heat treatments at temperatures in excess of 300 to 350° C.
A concave portion, such as a hole, a micro-flow passage or a micromixer, is formed on a surface of the glass substrate of the SOI substrate thus obtained and a surface treatment is performed using a silane coupling agent or the like, so that processes required for a DNA chip or a microfluidic chip are applied. In addition, a semiconductor element portion for the analysis/evaluation of a sample attached/held to this concave portion is formed in the SOI layer. Consequently, it is possible to obtain a microchip (biochip) in which a hole, a micro-flow passage or the like and a semiconductor element for analysis/evaluation are integrated into a single chip.
Furthermore, an insulating layer, such as a silicon dioxide film or a silicon nitride film, is formed on a surface of the SOI layer 12, a sample-holding portion to which a measurement sample is attached or held is provided on this insulating layer, and biasing electrodes used to form a depletion layer in a boundary face between the insulating layer and the SOI layer 12 and a signal-detecting circuit for detecting the amount of photoelectric current generated depending on the thickness of the depletion layer which varies according to the amount of charge provided by an analyte held by the sample-holding portion are further provided. Consequently, it is possible to obtain a macro chip, such as a surface potential sensor, capable of monitoring a change in the charge amount of a sample (for example, cell) from a detected photocurrent.
Hereinafter, constitutional examples of a microchip of the present invention will be described with reference to embodiments thereof.
Chip equipped with semiconductor element for fluorescence/absorbed light analysis:
Although only one concave portion 21 provided with the sensitive membrane 22 is illustrated in
On the other hand, in a predetermined part of the SOI layer 12, there is formed a semiconductor element portion 14 for analyzing/evaluating a sample (sensitive membrane 22 in the case of the present embodiment) attached/held to the concave portion 21. In the microchip illustrated in
In the semiconductor element portion 14, there are provided a light-receiving element for receiving fluorescence or absorbed light from the measurement sample, a photoelectric conversion element for converting the intensities of blank light (reference light which has transmitted through without being irradiated at the measurement sample) and light from the measurement sample into currents, and the like. This semiconductor element portion 14 generates an electrical signal corresponding to the light from the measurement sample and the blank light and the composition and structure of the measurement sample are identified on the basis of this signal.
LAPS-equipped chip:
In this figure, reference numeral 15 denotes an insulating layer formed on a surface of the SOI layer 12, reference numeral 16 denotes a sample-holding portion provided on the insulating layer 15, reference numeral 17a denotes a measurement sample, reference numeral 17b denotes a sensitive membrane, reference numerals 18a and 18b denote biasing electrodes used to form a depletion layer in a boundary face between the insulating layer 15 and the SOI layer 12, reference numeral 19 denotes a signal-detecting circuit for detecting the amount of photoelectric current generated depending on the thickness of the depletion layer which varies according to the amount of charge provided to the sensitive membrane 17b by the measurement sample, and reference numeral 60 denotes a semiconductor laser for generating electron-hole pairs within the depletion layer by means of light irradiation.
The sensor surface of this LAPS-equipped chip is the SOI layer 12 in which the insulating layer 15, such as oxide silicon, is formed, wherein a bias is applied to between the measurement sample 17a and the SOI layer 12 (substantially between the insulating layer 15 and the SOI layer 12) from the biasing electrodes 18a and 18b to form a depletion layer in a boundary face between the insulating layer 15 and the SOI layer. On the other hand, laser light from the semiconductor laser 60 is irradiated at the quartz substrate 20 from the rear surface thereof, thereby forming electron-hole pairs within the depletion layer. Under a biased environment in which a region near the boundary face between the insulating layer 15 and the SOI layer 12 is in a state of accumulation of electron-hole pairs, no photocurrents flow into an external circuit. However, if the region near the boundary face between the insulating layer 15 and the SOI layer 12 goes into an inverted state, the thickness of the depletion layer increases, thereby causing a photocurrent to flow into the external circuit.
If the amount of charge accumulated in the sensitive membrane 17b shown in
While aspects of the present invention have been described with reference to the embodiments thereof, it should be noted that the above-described embodiments are merely examples for carrying out the present invention and the present invention is not limited to these embodiments. Modifying these embodiments variously is within the scope of the present invention and it is obvious, from the foregoing description, that other various embodiments are possible within the scope of the present invention.
According to the present invention, it is possible to provide an SOI substrate having an SOI layer which has little defects and is superior in film uniformity, crystal quality, and electrical characteristics (carrier mobility and the like). In addition, use of this SOI substrate makes it possible to obtain a microchip (biochip) in which a hole, a micro-flow passage or the like and a semiconductor element for analysis/evaluation are integrated into a single chip, or a macro chip, such as a surface potential sensor, capable of monitoring a change in the charge amount of a sample (for example, cell).
Number | Date | Country | Kind |
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2006-067804 | Mar 2006 | JP | national |
Number | Date | Country | |
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Parent | 12281886 | Sep 2008 | US |
Child | 13476301 | US |