CN1836290A - Probe for an atomic force microscope - Google Patents
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- CN1836290A CN1836290A CN 200480023496 CN200480023496A CN1836290A CN 1836290 A CN1836290 A CN 1836290A CN 200480023496 CN200480023496 CN 200480023496 CN 200480023496 A CN200480023496 A CN 200480023496A CN 1836290 A CN1836290 A CN 1836290A
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技术领域technical field
本发明涉及原子力显微镜领域、这种显微镜中所使用的探针,以及操作这种显微镜的方法。特别地,涉及不利用探针高度的常规反馈控制的原子力显微镜。The present invention relates to the field of atomic force microscopy, probes used in such microscopes, and methods of operating such microscopes. In particular, it concerns atomic force microscopy that does not utilize conventional feedback control of probe height.
背景技术Background technique
原子力显微镜(AFM)或扫描力显微镜(SFM)由Binnig、Quate和Gerber在1986年发明。如同所有其他扫描探针显微镜,AFM基于在样品表面上方机械地扫描纳米探针以便获得样品的“相互作用图谱”的原理。该情况下的相互作用力仅是样品和粘连着悬臂弹簧的尖锐探针的尖端之间的分子相互作用。当探针尖端开始与样品紧密接近时,悬臂响应于相互作用力而弯曲。通过相对于探针扫描样品并测量作为横向位置的函数的悬臂偏转来收集图像。光杠杆技术通常用来测量该弯曲。因为悬臂遵守小位移的虎克定律,所以可以推导出尖端和样品之间的相互作用力。The atomic force microscope (AFM) or scanning force microscope (SFM) was invented in 1986 by Binnig, Quate and Gerber. Like all other scanning probe microscopes, AFM is based on the principle of mechanically scanning nanoprobes over the sample surface in order to obtain an "interaction map" of the sample. The interaction force in this case is only the molecular interaction between the sample and the tip of the sharp probe to which the cantilever spring is attached. When the probe tip comes into close proximity with the sample, the cantilever bends in response to the interaction force. Images were collected by scanning the sample relative to the probe and measuring cantilever deflection as a function of lateral position. Optical lever techniques are commonly used to measure this bending. Because the cantilever obeys Hooke's law for small displacements, the interaction force between the tip and the sample can be derived.
通常以两种模式中的一种操作AFM。在恒定力模式中,反馈允许定位压电驱动器响应于检测到的相互作用力的任何改变向上或向下移动样品(或探针)。这样,可以保持相互作用力相对稳定,并获得样品的相当可靠的形貌图像。可选地可以用恒定高度模式操作AFM。在扫描期间没有或几乎没有对样品或探针的垂直高度的调节。在本环境中,垂直高度的调节意味着在连接到悬臂式探针的传动器或样品本身上施加转变。因此当悬臂弯曲的程度改变时,探针尖端还有自由度向上或向下移动。在恒定高度模式中,不能区分开样品的形貌改变和相互作用力变化,因为任一个或两者都会导致悬臂弹簧弯曲。AFMs are typically operated in one of two modes. In constant force mode, feedback allows the positioning of the piezoelectric actuator to move the sample (or probe) up or down in response to any change in the detected interaction force. In this way, the interaction forces can be kept relatively stable and a fairly reliable topographical image of the sample can be obtained. Optionally the AFM can be operated in constant altitude mode. There is little or no adjustment to the vertical height of the sample or probe during scanning. In this context, adjustment of the vertical height means imposing a transition on the actuator attached to the cantilever probe or on the sample itself. Thus, the probe tip also has freedom to move up or down when the degree of cantilever bending is changed. In constant-height mode, it is not possible to distinguish between changes in the topography of the sample and changes in the interaction force, since either or both will cause the cantilever spring to bend.
除了这些不同反馈机制之外,通常以三种不同方式中的一种来获得图像对比度。在接触模式中,当扫描进行时尖端和样品保持紧密接触,即保持分子相互作用的排斥机制。在轻敲模式中,传动器驱动悬臂以其共振频率作“轻敲”运动。因此,探针尖端仅在其振荡(轻敲)周期的非常小部分中接触表面。该显著缩短的接触时间意味着样品上的横向力大大地减小,因此当进行扫描时探针对样品的破坏性较小。因此它广泛用于成像敏感生物样品。一般地使用反馈机制保持振荡幅度恒定。在非接触操作中,悬臂在样品上方分子相互作用力不再排斥的距离处振荡。但是该操作模式在实际中非常难实施。In addition to these different feedback mechanisms, image contrast is typically achieved in one of three different ways. In contact mode, the tip and sample remain in close contact while scanning is performed, ie the repulsive mechanism that maintains molecular interactions. In tapping mode, the actuator drives the boom in a "tapping" motion at its resonant frequency. Thus, the probe tip only touches the surface during a very small portion of its oscillation (tapping) cycle. This significantly shortened contact time means that the lateral force on the sample is greatly reduced and therefore the probe is less destructive to the sample when scanning. It is therefore widely used for imaging sensitive biological samples. Typically a feedback mechanism is used to keep the oscillation amplitude constant. In non-contact operation, the cantilever is oscillated at a distance above the sample at which molecular interaction forces are no longer repulsive. But this mode of operation is very difficult to implement in practice.
探针显微镜学的新进展已导致快得多的数据收集时间。使用更快的扫描技术,例如PCT专利申请公布WO 02/063368号中所描述的,有限的探针响应度日益成为图像收集时间的限制因素。探针不能瞬间响应样品特征的改变,因此例如在探针遇到具有增加高度的样品表面区域和系统对它作反应之间存在固有的时间延迟。该缺点适用于AFM操作的恒定力和恒定高度模式。在恒定高度模式中不那么严重,因此对于快速扫描技术恒定高度模式是优选操作模式,但是它仍然足以不适当地限制当前世代快速扫描探针显微镜的扫描速度。New advances in probe microscopy have resulted in much faster data collection times. With faster scanning techniques, such as that described in PCT Patent Application Publication No. WO 02/063368, limited probe responsivity is increasingly becoming the limiting factor in image collection time. Probes cannot respond instantaneously to changes in sample characteristics, so for example there is an inherent time delay between the probe encountering a sample surface area of increasing height and the system reacting to it. This shortcoming applies to the constant-force and constant-altitude modes of AFM operation. It is less severe in constant height mode, so for fast scanning techniques constant height mode is the preferred mode of operation, but it is still enough to unduly limit the scan speed of current generation fast scanning probe microscopes.
在恒定力AFM模式中,通常利用电子反馈机制以便保持平均相互作用力恒定。当扫描进行时,如果相互作用力改变(例如由样品高度的改变引起的),首先通过探测电子装置探测到的探针响应的改变观察到这点,产生误差(例如,设定点减去偏转)并且使用反馈回路通过调节探针或样品位置使误差达到最小。反馈回路具有与之关联的时间常数,它对能够收集完整图像的最终速度施加限制。In constant force AFM mode, an electronic feedback mechanism is typically utilized in order to keep the average interaction force constant. As the scan progresses, if the interaction force changes (e.g., caused by a change in sample height), this is first observed by a change in the probe response detected by the detection electronics, generating an error (e.g., set point minus deflection ) and use a feedback loop to minimize error by adjusting the probe or sample position. The feedback loop has a time constant associated with it that imposes a limit on the ultimate speed at which a complete image can be collected.
如果以恒定高度模式工作,该问题并不是那么限制性的,其中通常并不利用电子反馈达到恒定力AFM中所使用的程度。但是对于要准确测量的相互作用力,探针尖端应当尽可能跟踪样品表面的等高线。这点通过利用当悬臂被样品表面弯曲时所引发的反作用力来保证。也就是,当扫描样品表面的高区域时,悬臂愈加向上弯曲,并且弹簧中所储存的能量增加。当高度落下时,回复力将悬臂推回向其平衡(平直)位置,从而保持与表面接触。但是如果扫描速度太快,探针将不能跟踪表面,而是被有力地掷向表面的任何凸起的上方并可能开始共振或“共鸣”。这又引起成像相互作用力的振荡。类似地,当高度落下时,回复力可能不够大以保证探针尖端保持与表面接触,从而将丢失在该图像区域表面周围的信息。This problem is not so restrictive if operating in constant altitude mode, where electronic feedback is generally not utilized to the extent used in constant force AFM. But for the interaction force to be measured accurately, the probe tip should track the contours of the sample surface as closely as possible. This is ensured by utilizing the reaction force induced when the cantilever is bent by the sample surface. That is, when scanning high regions of the sample surface, the cantilever bends upward more and more, and the energy stored in the spring increases. When the height is dropped, the restoring force pushes the cantilever back towards its equilibrium (flat) position, thereby maintaining contact with the surface. But if the scanning speed is too fast, the probe will not be able to track the surface, but will be thrown forcefully over any bumps on the surface and may start to resonate or "resonate". This in turn causes oscillations in the imaging interaction force. Similarly, when the height is dropped, the restoring force may not be strong enough to ensure that the probe tip remains in contact with the surface, and information around the surface in that image area will be lost.
上面提到的WO 02/063368描述一种扫描探针显微镜,其中样品或探针安装到共振器上,并且通过以共振频率或接近于共振频率驱动共振器,可以相对于探针扫描样品。共振器典型地将具有类似于探针的共振频率的几十kHz的共振频率。因此像素之间的典型时间间隔比1/fr更短,其中fr是探针的共振频率。另一方面,响应于样品表面的形貌改变所花的时间(τres)基于探针的有效质量和悬臂的弹簧常数。如果τres>fr,那么显然地不能从一个像素到另一个像素准确地测量相互作用力。WO 02/063368 mentioned above describes a scanning probe microscope in which the sample or probe is mounted on a resonator and by driving the resonator at or close to the resonant frequency the sample can be scanned relative to the probe. The resonator will typically have a resonant frequency of a few tens of kHz similar to that of the probe. The typical time interval between pixels is thus shorter than 1/ fr , where fr is the resonance frequency of the probe. On the other hand, the time taken to respond to a change in topography of the sample surface (τ res ) is based on the effective mass of the probe and the spring constant of the cantilever. If τ res > f r , then obviously the interaction force cannot be measured accurately from one pixel to another.
认识到有需要提供对样品形貌起伏或对相互作用力变化的改进探针响应度,以便允许在图像赝象例如由探针共鸣或表面的不良跟踪导致的那些赝象开始退化图像品质之前,以更快的扫描速度执行AFM显微镜方法。Recognizing that there is a need to provide improved probe responsivity to sample topography fluctuations or to changes in interaction forces in order to allow image artifacts such as those caused by probe resonance or poor tracking of surfaces before they begin to degrade image quality, Perform AFM microscopy methods at faster scan speeds.
发明内容Contents of the invention
本发明提供一种供原子力显微镜或供纳米光刻术使用的探针,该探针包括连接到具有100nm或更小针尖半径的探针尖端的力感测元件,其特征在于改进探针,使得当受到外加力时,偏置力以大于当探测样品时由探针尖端的位移引起的回复力的量值将探针尖端和样品的任一个或两者推向彼此。The present invention provides a probe for atomic force microscopy or for use in nanolithography comprising a force sensing element attached to a probe tip having a tip radius of 100 nm or less, characterized in that the probe is modified such that When subjected to an applied force, the biasing force pushes either or both the probe tip and sample toward each other by a magnitude greater than the restoring force caused by the displacement of the probe tip when probing the sample.
在认识到本发明的范围之后,考虑现有技术原子力显微镜中当典型悬臂式探针与样品表面接触时所涉及的力是有用的。因此现在参考图1说明这点。Having appreciated the scope of the present invention, it is useful to consider the forces involved in prior art atomic force microscopy when a typical cantilever probe comes into contact with a sample surface. This is therefore now explained with reference to FIG. 1 .
在图1中,显示了被原子力显微镜(AFM)的探针扫描的样品1。探针包括从中伸出悬臂3的基片2,悬臂3具有安装在远离基片2那端的针尖半径为100nm或更小的尖锐探测纳米尖端4。为扫描做准备时,经由探针到AFM的安装在探针基片端2施加向下力(Fexternal)到探针上,移动探针尖端4与样品1接触。为了在扫描期间保持接触,力Fexternal大于仅仅使尖端4开始与样品1接触所需的力。结果当扫描样品时,悬臂3从其静止位置5向上弯曲。In FIG. 1 , a sample 1 scanned by the probe of an atomic force microscope (AFM) is shown. The probe comprises a
在简化模型中,可以认为悬臂3遵守小位移的虎克定律。因此当加力于样品上时,如果弯曲程度使得将尖端4从其静止位置移动垂直距离x,并且悬臂弹簧常数为k,那么悬臂所施加的回复力是kx。因此尖端4所施加的使它保持跟踪表面的向下力与kx成正比。In the simplified model, it can be considered that the
显然地,探针尖端4的响应度从而AFM技术的分辨率依赖于悬臂3施加到样品1上的力kx的程度。探针和表面之间的力越大,对表面变化的响应度越大。这表明高弹簧常数k是合乎需要的,特别是如果要快速扫描时。另一方面,力越大,探针越可能损伤样品。因此,现有技术AFM悬臂探针必须在探针响应度和损伤样品的可能性之间做出基本的权衡。Apparently, the responsivity of the
但是根据本发明的探针被改进了,使得当扫描样品时,它受到显著大于探针施加到样品上的回复力kx的偏置力。这允许它更好地跟踪样品表面并且更快扫描是可能的。随后将更详细地看到,本发明所需要的以偏置力超过回复力通过在探针上包括响应于外加力的偏置元件和/或减小悬臂梁的弹簧常数来实现。But the probe according to the invention is modified so that when scanning the sample it is subjected to a biasing force which is significantly greater than the restoring force kx exerted by the probe on the sample. This allows it to better track the sample surface and faster scans are possible. As will be seen in more detail later, the need for the present invention to exceed the restoring force with a biasing force is achieved by including a biasing element on the probe that is responsive to an applied force and/or reducing the spring constant of the cantilever beam.
和图像收集可能花费多于30秒的常规AFM不同,使用本发明,样品的毫秒成像是可能的。例如,22.4cms-1的尖端速度允许以128×128像素用14.3ms成像4.4×4.4微米的区域和用8.3ms成像1.5×1.5微米的区域。此外,即使在该速度下,用软聚合物表面可获得具有比10nm横向和1nm竖向更好分辨率的图像。Unlike conventional AFM where image collection may take more than 30 seconds, with the present invention millisecond imaging of the sample is possible. For example, a tip speed of 22.4 cms -1 allows imaging a 4.4 x 4.4 micron area in 14.3 ms and a 1.5 x 1.5 micron area in 8.3 ms at 128 x 128 pixels. Furthermore, even at this speed, images with better resolution than 10 nm laterally and 1 nm vertically can be obtained with soft polymer surfaces.
在本发明一种实施方案中,偏置元件例如可以是响应于外加磁力的磁性元件,或连接到电源一端从而允许在探针和样品之间引发电压电势的导电元件。在这两种情况中,偏置力(磁的或静电的)的极性使得它将探针和样品推向彼此。此外,施加到探针上的偏置力的量值与其偏转程度无关。这样,因为探针梁具有非常低的弹簧常数,与偏置力相比,弯曲/偏转回复力是非常小的,所以尖端到表面上的力实际上是与偏转无关的。In one embodiment of the invention, the biasing element may be, for example, a magnetic element responsive to an applied magnetic force, or a conductive element connected to one end of a power supply to allow a voltage potential to be induced between the probe and the sample. In both cases, the polarity of the biasing force (magnetic or electrostatic) is such that it pushes the probe and sample towards each other. Furthermore, the magnitude of the biasing force applied to the probe is independent of its degree of deflection. Thus, because the probe beam has a very low spring constant, the bending/deflection restoring force is very small compared to the biasing force, so the tip-to-surface force is virtually deflection independent.
已特殊地制造现有技术AFM探针,使得响应于外偏置力。例如,EP 872707描述一种包括压电元件的悬臂探针。将控制信号发送到压电元件,以便向上推动探针远离样品,使得胜过吸力。类似地,US 5,515,719描述一种包括磁性粒子的探针,磁性粒子响应于螺线管控制的磁场使得拉动探针远离样品表面。如前面,本专利的焦点在于防止探针被吸引到样品表面上而导致损伤。Prior art AFM probes have been specially fabricated so as to respond to external biasing forces. For example, EP 872707 describes a cantilever probe comprising piezoelectric elements. A control signal is sent to the piezoelectric element in order to push the probe upwards away from the sample such that the suction force is overcome. Similarly, US 5,515,719 describes a probe comprising magnetic particles which, in response to a solenoid-controlled magnetic field, pull the probe away from the sample surface. As before, the focus of this patent is to prevent probes from being attracted to the sample surface and causing damage.
专利申请公布WO 99/06793号中所公开的悬臂探针也包括磁性元件。但是,该方案中的磁场用来控制探针-样品距离,并且根据期望的隔离而改变。这与本发明所使用的磁场方案形成对比。在扫描期间,该实例中提供到尖端的力是恒定的,这只是为了如果失去接触加速尖端返回样品表面的目的。在US专利5,670,712号中描述包括响应于可调节磁场的探针的另一种系统。由设置来将悬臂偏转保持在恒定水平的反馈回路控制场幅度。并且这与根据本发明的固有地允许改变偏转程度的AFM探针形成对比。没有这种运动自由,不能跟踪样品表面的等高线和测量相互作用力,这违背本发明的整个目的。The cantilever probe disclosed in Patent Application Publication No. WO 99/06793 also includes a magnetic element. However, the magnetic field in this scheme is used to control the probe-sample distance and is varied according to the desired isolation. This is in contrast to the magnetic field scheme used in the present invention. During scanning, the force provided to the tip is constant in this example only for the purpose of accelerating the tip's return to the sample surface if contact is lost. Another system including a probe responsive to an adjustable magnetic field is described in US Patent No. 5,670,712. The field amplitude is controlled by a feedback loop set up to maintain the cantilever deflection at a constant level. And this is in contrast to AFM probes according to the present invention which inherently allow varying degrees of deflection. Without this freedom of movement, it is impossible to follow the contours of the sample surface and measure the interaction forces, which defeats the whole purpose of the invention.
在可选方法中,悬臂梁设计成具有低品质(或Q)因子。与高Q因子梁相比,这增加消散机械能的速率。如果在扫描期间放置在这种梁上的探针敲震远离表面,任何作为结果产生的机械振荡被减小,并且探针将快速返回以跟踪样品表面。在一种实施方案中,通过将适合于消散能量的涂料涂敷到梁上减小悬臂梁的Q因子,否则能量将通过一个或多个振荡模式的激发而机械地储存于梁中。因此,与对等的无涂敷梁相比,对于其振荡模式的一个或多个,支撑梁的Q因子被降低。涂料优选地是涂敷到探针至少一侧的吸收能量材料,例如聚合物膜。In an alternative approach, the cantilever beam is designed to have a low quality (or Q) factor. This increases the rate at which mechanical energy is dissipated compared to high Q factor beams. If a probe placed on such a beam is knocked away from the surface during scanning, any resulting mechanical oscillations are dampened and the probe will snap back to track the sample surface. In one embodiment, the Q-factor of the cantilever beam is reduced by applying a coating to the beam that is suitable for dissipating energy that would otherwise be mechanically stored in the beam through excitation of one or more oscillatory modes. Thus, the Q-factor of the supported beam is reduced for one or more of its modes of oscillation compared to an equivalent uncoated beam. The coating is preferably an energy absorbing material, such as a polymer film, applied to at least one side of the probe.
显然地,如果将它改进成受到外部引导力并具有低Q因子,通过本发明探针的样品跟踪被最好地实现。但是在某些环境中,这些特征中只有一个是必需的。当探针被带到样品附近时,认为将形成连接两者的毛细管颈。特别地,如果探针的Q因子足够低,已经发现由毛细管颈引起的偏置力形成支配回复力。类似地,如果施加较强的偏置力,梁的Q因子不需要那么低。在该实例中认为经由探针与样品表面的相互作用也可以发生机械能的消散。Apparently, sample tracking by the probe of the present invention is best achieved if it is modified to be externally guided and have a low Q-factor. But in some environments, only one of these characteristics is required. When the probe is brought into the vicinity of the sample, it is believed that a capillary neck will form connecting the two. In particular, it has been found that the biasing force induced by the capillary neck forms the dominant restoring force if the Q-factor of the probe is sufficiently low. Similarly, the Q-factor of the beam does not need to be as low if a stronger biasing force is applied. It is considered in this example that dissipation of mechanical energy may also occur via interaction of the probe with the sample surface.
具有涂层的AFM悬臂在现有技术中公开,虽然都不是涂敷适合于阻尼机械振荡的材料。上面提及的US 5,515,719公开一种通过它力可以施加到悬臂上的磁性涂层。US 6,118,124和US 6,330,824都描述了用于探测辐射的涂敷悬臂。因此涂层受辐射影响,通过悬臂性质的定量改变来测量辐射强度。这与本发明的涂层材料形成对比,本发明的涂层材料不受入射辐射影响,但吸收机械能。AFM cantilevers with coatings are disclosed in the prior art, although none are coated with a material suitable for damping mechanical oscillations. US 5,515,719 mentioned above discloses a magnetic coating through which force can be applied to the cantilever. US 6,118,124 and US 6,330,824 both describe coated cantilevers for detecting radiation. The coating is thus affected by the radiation, and the intensity of the radiation is measured by a quantitative change in the properties of the cantilever. This is in contrast to the coating material of the present invention, which is not affected by incident radiation but absorbs mechanical energy.
在可选方面,本发明提供一种根据样品和探针之间的相互作用力成像样品的原子力显微镜,该显微镜包括布置来提供探针和样品表面之间的相对扫描动作,并能够使样品和探针紧密接近以足够在它们之间建立可探测相互作用的驱动装置;以及In an alternative aspect, the invention provides an atomic force microscope for imaging a sample based on the interaction forces between the sample and the probe, the microscope comprising an arrangement to provide a relative scanning motion between the probe and the sample surface and enabling the sample and the probes are in close enough proximity to the actuation means to establish a detectable interaction between them; and
布置来测量探针的偏转和/或位移的探针检测机构;a probe detection mechanism arranged to measure deflection and/or displacement of the probe;
特征在于显微镜包括上述探针。It is characterized in that the microscope comprises the above-mentioned probe.
可选地,显微镜特征在于,它包括被布置使得在操作中将力(Fdirect)施加到样品或探针的任一个或两个上或施加到样品和探针之间的力(Fdirect)产生装置,控制力(Fdirect)使得将探针推向样品,反之亦然。Optionally, the microscope is characterized in that it comprises a force (F direct ) arranged such that in operation a force (F direct ) is exerted on either or both of the sample or the probe or between the sample and the probe Means are generated to control the force (F direct ) such that the probe is pushed towards the sample and vice versa.
在又一个方面,本发明提供一种从具有纳米特征的样品的扫描区域中收集图像数据的方法,其中该方法包括步骤:In yet another aspect, the present invention provides a method of collecting image data from a scanned region of a sample having nanofeatures, wherein the method comprises the steps of:
(a)将探针移动到与样品紧密接近,使得允许在探针和样品之间建立相互作用力,其中探针包括具有100nm或更小针尖半径的尖端的支撑梁;(a) moving the probe into close proximity to the sample such that an interaction force is allowed to be established between the probe and the sample, wherein the probe comprises a support beam having a tip with a tip radius of 100 nm or less;
(b)使在样品和探针之间建立力(Fdirect),使得推动探针移向样品,反之亦然;(b) causing a force (F direct ) to be established between the sample and the probe such that the probe is pushed towards the sample and vice versa;
(c)扫描跨越样品表面的探针或在探针下方的样品,同时提供探针和表面之间的相对动作,使得扫描线的布局覆盖扫描区域;(c) scanning the probe across the surface of the sample or the sample below the probe while providing relative motion between the probe and the surface such that the scan lines are arranged to cover the scan area;
(d)测量探针的偏转和/或位移;以及(d) measuring probe deflection and/or displacement; and
(e)处理步骤(d)中获得的测量值,以便提取与样品的纳米结构相关的信息。(e) processing the measurements obtained in step (d) in order to extract information relating to the nanostructure of the sample.
附图说明Description of drawings
现在将仅作为例子并参考附图描述本发明的实施方案。Embodiments of the invention will now be described, by way of example only, with reference to the accompanying drawings.
图1是在现有技术原子力显微镜中当悬挂式探针与样品表面接触时所涉及的力的图示说明。Figure 1 is a graphical illustration of the forces involved when a suspended probe comes into contact with a sample surface in a prior art atomic force microscope.
图2显示包括根据本发明第一实施方案的探针的原子力显微镜的示意实施。Figure 2 shows a schematic implementation of an atomic force microscope comprising a probe according to a first embodiment of the invention.
图3显示包括根据本发明第二实施方案的探针的原子力显微镜的示意实施。Figure 3 shows a schematic implementation of an atomic force microscope comprising a probe according to a second embodiment of the invention.
图4显示包括根据本发明第三实施方案的探针的原子力显微镜的示意实施。Figure 4 shows a schematic implementation of an atomic force microscope comprising a probe according to a third embodiment of the invention.
图5显示包括根据本发明第四实施方案的探针的原子力显微镜的示意实施。Figure 5 shows a schematic implementation of an atomic force microscope comprising a probe according to a fourth embodiment of the invention.
图6显示包括根据本发明第五实施方案的探针的原子力显微镜的示意实施。Figure 6 shows a schematic implementation of an atomic force microscope comprising a probe according to a fifth embodiment of the invention.
图7显示包括根据本发明第六实施方案的探针的原子力显微镜的示意实施。Figure 7 shows a schematic implementation of an atomic force microscope comprising a probe according to a sixth embodiment of the invention.
图8是在图2至7的AFM中当探针与样品表面接触时所涉及的力的图示说明。Figure 8 is a graphical illustration of the forces involved when the probe is in contact with the sample surface in the AFM of Figures 2-7.
图9a和9d是使用根据本发明的探针生成的结晶聚环氧乙烷(PEO)样品的两个分离表面区域的AFM图像。Figures 9a and 9d are AFM images of two isolated surface regions of a crystalline polyethylene oxide (PEO) sample generated using probes according to the invention.
图9b,9c,9e和9f是跟图9a和9d相同的表面区域的常规AFM图像。Figures 9b, 9c, 9e and 9f are conventional AFM images of the same surface area as Figures 9a and 9d.
图10说明本发明探针的预定悬臂设计的例子。Figure 10 illustrates an example of a predetermined cantilever design for a probe of the present invention.
图11和12说明预定悬臂中具有低和受控弹簧常数的区域的形成。Figures 11 and 12 illustrate the formation of a region with a low and controlled spring constant in a predetermined cantilever.
具体实施方式Detailed ways
参考图2显示了一般地用10指示的AFM的示意实施,它使用根据本发明一个方面构造的探针的第一实施方案。所示的AFM装置10包括适合于承载样品14的并安装在音叉16一个叉臂上的平板12。音叉16连接到压电转换器18和粗驱动装置20。压电转换器18用来在三个维度x,y和z方向上驱动样品14(连同平板12和音叉16)。本领域中通常地取笛卡尔坐标系统的z轴与样品14所占据的平面垂直。也就是,相互作用力不仅依赖于探针22在样品14上方的xy位置(成像的像素),而且依赖于它在上方的高度。布置音叉控制(没有显示)以将正弦电压施加到音叉16上,以便在xy平面内激发共振或近共振振动。可选地,平板12和音叉16可以支撑在振动隔离台32上,以便将音叉16的振动与显微镜的其余部分隔离。但是,在使用该探针的显微镜所考虑的图像频率下,与较低图像频率相比外部噪声已不成问题,所以可以省却振动隔离台。探针22是小质量AFM探针,在扫描期间,在探针尖端22a和样品表面之间引发相互作用力。布置探针检测机构28以便测量指示相互作用力强度的探针尖端22a的位移或支撑尖端的梁22b的弯曲。由探针检测机构28收集的数据被分析并输出到显示器30。Referring to Figure 2 there is shown a schematic implementation of an AFM, indicated generally at 10, using a first embodiment of a probe constructed in accordance with an aspect of the present invention. The
一般地,现有技术悬臂探针用硅或氮化硅制成,这使得容易使用成熟的硅微制造技术制造它们。但是,和现有技术悬臂探针不同,根据本发明的探针22具有涂敷到探针的支撑梁22b的聚合物涂层22c。如随后将更详细地说明,该涂层22c用来驱散能量,否则能量通过振荡模式的激发机械地储存于探针中,从而与不存在涂层22的相同梁相比对于其振动模式的一个或多个降低支撑梁的Q因子。Typically, prior art cantilever probes are made of silicon or silicon nitride, which makes it easy to fabricate them using well-established silicon microfabrication techniques. However, unlike prior art cantilever probes, the probe 22 according to the present invention has a
在使用装置10获取图像时,首先使用粗驱动装置20使样品14与探针22接触。用压电驱动器18进行细高度和初始起动位置调节,同时探针检测机构28测量作为探针22和样品14相互作用力的结果的探针弯曲。一旦测量的弯曲达到期望水平,扫描探针22下方的样品表面。当扫描探针22下方的样品14时,设置音叉16使得向图的平面内和外(y轴)振动。这使安装样品的平台振荡。同时,压电驱动器18在垂直(x)方向上调动样品14。样品振荡具有几微米量级的相当大的振幅。在扫描期间,探针检测机构28连续地获得读数,如作为本领域标准的,这可以基于光杠杆技术:使用从探针反射的激光测量探针弯曲。探针检测机构28的输出信号直接提供到处理器和显示器30。In acquiring an
如上所述,图2中所示的探针22与现有技术中的不同在于它涂敷有聚合物材料22c。涂层22c可以在一侧或两侧,只要材料本身适合于消散否则会储存于探针中的能量。As mentioned above, the probe 22 shown in Figure 2 differs from the prior art in that it is coated with a
Q因子是无量纲量,它可以用来量化振荡器的消散(或阻尼)。它具有性质:The Q factor is a dimensionless quantity that can be used to quantify the dissipation (or damping) of an oscillator. It has the properties:
Q=储存于振荡器中的能量/每弧度消散的能量Q = energy stored in the oscillator / energy dissipated per radian
储存的能量被快速消散的强阻尼系统具有低Q,而轻阻尼系统具有高Q。由Si和SiN材料制成的振荡器不具有太多内损耗,结果大部分商业上可获得的AFM悬臂将具有高Q,在空气中典型地为5-500的量级。此外,如果设计以供轻敲模式中使用,悬臂具有高Q是有利的。在该模式中,在共振下驱动悬臂,并且在许多个振荡周期上测量相互作用力。通过使振荡周期上的能量损失达到最小,因此高Q担当机械滤波器。Strongly damped systems, where the stored energy is quickly dissipated, have a low Q, while lightly damped systems have a high Q. Oscillators made of Si and SiN materials do not have much internal loss, as a result most commercially available AFM cantilevers will have a high Q, typically on the order of 5-500 in air. Furthermore, it is advantageous for the cantilever to have a high Q if designed for use in tapping mode. In this mode, the cantilever is driven at resonance and the interaction force is measured over a number of oscillation cycles. The high Q acts as a mechanical filter by minimizing energy loss over the oscillation period.
机械振荡器具有许多共振振荡模式,并且这些模式的每个的品质因子可以依赖于与频率相关的材料性质和振荡器的形状而不同。当在这里提及Q因子时,我们指的是关于这些模式的任一个的探针的Q因子,或者指的是一组模式的Q因子。A mechanical oscillator has many resonant modes of oscillation, and the quality factor of each of these modes can differ depending on the frequency-dependent material properties and the shape of the oscillator. When referring to a Q-factor here, we mean the Q-factor of a probe for any of these modes, or the Q-factor of a set of modes.
但是在本发明的情况中,在高速原子力显微镜中使用具有低Q的探针是合乎需要的。如果探针具有高Q,将花费长时间响应改变,并且如果给予刺激因素如扫过样品表面上的高形貌时所提供的,它将以共振模式的组合共鸣。本探针依靠其涂层22c被设计成具有低Q。理想地,Q因子足够低,使得任何激发的振荡被严格地阻尼。低品质因子的使用意味着几乎没有能量能够储存在探针的支撑梁中,所以当被撞击时例如当在样品表面的高区域上方扫描时,探针不会长时间“共鸣”。这允许更快地返回样品表面,从而在扫描期间更好的跟踪。But in the context of the present invention, it is desirable to use probes with low Q in high speed atomic force microscopy. If the probe has a high Q, it will take a long time to respond to changes, and if given a stimulus such as that provided by sweeping high topography on the sample surface, it will resonate in a combination of resonant modes. The present probe is designed to have a low Q by virtue of its
探针上的涂层用来消散否则将储存于探针中的机械能。与没有涂层的探针相比,具有涂层的探针将储存较少机械能,并且与不存在涂层时相比,在某个具体时间处具有涂层的探针的运动将与该具体时间处探针尖端下方的表面关联更紧密。The coating on the probe serves to dissipate mechanical energy that would otherwise be stored in the probe. A probe with a coating will store less mechanical energy than a probe without a coating, and the motion of a coated probe at a specific time will correspond to that specific time compared to when no coating is present. The surface below the probe tip at time is more closely associated.
依赖于成像的样品和选择的扫描速度,可能在成像期间最可能激发比第一或基本模式更高的模式。在该情况下,选择涂层以保证该模式的Q因子显著地减小。通过调节涂层的能量吸收和消散性质,减小或消除最可能妨碍图像品质的探针的振荡,同时使探针质量的改变达到最小是可能的。Depending on the sample being imaged and the scan speed chosen, it may be that modes higher than the first or fundamental mode are most likely to be excited during imaging. In this case, the coating is chosen to ensure that the Q-factor of this mode is significantly reduced. By adjusting the energy absorbing and dissipating properties of the coating, it is possible to reduce or eliminate the oscillations of the probe most likely to impede image quality, while minimizing changes in probe mass.
许多聚合物材料可以用来提供涂层22c,并且具体选择的时机对于本领域技术人员将是显然的。根据其粘弹性性质选择材料:它必须足够弹性以便保持其形状为涂敷悬臂的膜,同时执行其消散机械能的任务。主要通过在分子级上依赖于聚合物链和其环境的摩擦系数的粘性机制而发生机械能的消散。理想涂层是具有程度刚好足以保持涂层粘合的低交叉链接密度的橡胶。交叉链接可以如同常规橡胶那样是化学的,或者如同热塑性弹性体那样是物理的。已经发现了涂敷在AFM支撑梁的两侧上的多数组分是具有低于室温的玻璃转变温度的无定形橡胶块体且少数组分是具有高于室温的玻璃转变温度的无定形聚合物的共聚物材料当在室温下使用时显著地改进其跟踪能力。通过溶液浇铸涂敷共聚物。也就是,包含聚合物的溶液滴在高温下置于支撑梁上以便赶走溶剂。也可以使用其他热塑性弹性体。已经发现了这种方案允许探针甚至以例如WO 02/063368中所描述的共振振荡速度跟踪样品表面。A number of polymeric materials can be used to provide
关于所采用的聚合物材料和涂敷方法的考虑在某种程度上限制可用的选择。基本想法是用理想地不会不当地影响探针的其他性质如质量、尖端形状等的吸收能量材料涂敷支撑梁。已经发现了用上述共聚物溶液浇铸支撑梁伴随可接受的质量增加但增强能量消散。但是可以使用其他涂敷方法。这些包括:在电解池中将带电聚合物“拖曳”到支撑梁上;用化学方法加标签于聚合物上(例如用硫醇基)并利用它与支撑梁材料或支撑梁上金属涂层(例如硫醇化学情况下的金)的反应将聚合物附着到支撑梁上。Considerations regarding the polymeric material employed and the method of application somewhat limit the options available. The basic idea is to coat the support beam with an energy absorbing material that ideally does not unduly affect other properties of the probe, such as mass, tip shape, etc. Casting of support beams with the above copolymer solutions has been found to be accompanied by acceptable mass gain but enhanced energy dissipation. However, other coating methods can be used. These include: "dragging" charged polymers onto support beams in an electrolytic cell; chemically labeling polymers (e.g. with thiol groups) and using it to interact with support beam materials or metal coatings on support beams ( A reaction such as gold in the case of thiol chemistry) attaches the polymer to the support beam.
如先前所述,AFM悬臂上的聚合物涂层是已知的。但是这种现有技术涂层材料根据它们的化学性质而选择,以便允许入射辐射的检测。也就是,材料必须具有优先吸收特定频率下的能量的化学键。这种材料将不适合于具有适合于供高速显微镜使用的效率的机械能消散。As mentioned previously, polymer coatings on AFM cantilevers are known. But such prior art coating materials are chosen according to their chemical nature in order to allow detection of incident radiation. That is, the material must have chemical bonds that preferentially absorb energy at specific frequencies. Such a material would not be suitable for mechanical energy dissipation with an efficiency suitable for use with high speed microscopy.
将涂层22c涂敷到假设是小尺寸的支撑梁的两侧实际上要比仅涂敷一侧稍微容易实现。但是优选地更接近样品的支撑梁一侧留着不涂敷。单侧涂敷足以减小储存在探针中的机械能,并且减小当探针接触时任何涂层材料污染样品的可能性。Applying the
理想地,用于涂层22c的聚合物材料在预期使用探针的温度下和在支撑梁的主要共振模式的频率范围中将在其能量损失谱中具有峰。典型地,因此它应当是橡胶性聚合物。可选地,也可以使用具有高组分的橡胶性聚合物的共聚物或其他复合物。Ideally, the polymeric material used for
如果涂敷到悬臂中的横隙,则可以增加聚合物涂层的能量消散。也就是,如果薄聚合物膜桥接悬臂中的孔洞,膜将既用来内部消散能量,又用来增加与周围流体媒介如空气的相互作用面积。从而通过该途径增加粘性能量消散,同时使悬臂的弹簧常数达到最小。The energy dissipation of the polymer coating can be increased if applied to the transverse gap in the cantilever. That is, if a thin polymer membrane bridges the holes in the cantilever, the membrane will serve both to dissipate energy internally and to increase the interaction area with the surrounding fluid medium, such as air. The viscous energy dissipation is thus increased through this approach while minimizing the spring constant of the cantilever.
图3显示一般地用10指示的AFM的示意实施,它使用根据本发明构造的探针的第二实施方案。AFM装置10与图2中所示的非常类似,并且类似地标示两个系统中共有的组件。如前面一样,承载样品14的平板12安装在xy平面内以共振或近共振振动驱动的音叉16的一个叉臂上。在三个维度x,y和z方向上扫描样品14(连同平板12和音叉16),并且所引发的相互作用力不仅依赖于探针22在样品14上方的xy位置(成像的像素),而且依赖于它在上方的高度。探针22的悬臂组件在两侧涂敷有聚合物膜,并被定形使得具有小于1NM-1的低弹簧常数。但是跟图2中所示的悬臂不同,根据本发明该实施方案的探针22额外具有安装在尖端22a上方的磁性元件24(图3中所示的圆珠)。并且,磁体26包含于AFM中例如在平板12下方,以便提供强度足以在磁珠24上施加力的磁场。力可以经由施加到探针上的磁矩或通过磁场梯度。如同图2中所示的装置10,布置探针检测机构18,以便测量探针22的弯曲。由探针检测机构28收集的数据被分析并输出到显示器30。Figure 3 shows a schematic implementation of an AFM, indicated generally at 10, using a second embodiment of a probe constructed in accordance with the present invention. The
在使用装置10获取图像时,建立相互作用力的接触机制和扫描技术与关于图2的装置10所描述的基本相同。但是一旦建立期望的相互作用力水平从而探针的支撑梁22b的弯曲,那么图2装置10中不存在的磁体26被接通,并且在探针尖端22a的附近产生磁场B。磁珠24与该磁场相互作用,引导磁场使得所产生磁力将磁珠24向下吸引向样品14。因此通过该磁力的引导动作,探针尖端22a保持与样品14接触。当磁场B开通时,(以调谐音叉-样品台的共振频率)振荡样品表面并在探针22下方扫描样品表面,并且如同前面一样处理输出信号。When using
图4至图7显示一般地用10指示的可选AFM的示意实施,它使用根据本发明构造的探针的更多实施方案。在每种情况中,AFM装置10与图2和3中所示的非常类似,并且类似地标示所有装置共有的组件。如同前面一样,样品14安装在平板12上。与图2和3所示的实施方案不同,在图4,5,6和7中,探针22安装在音叉16一个叉臂上,并且探针相对于样品的接近控制以及粗细定位由转换器18,20如压电转换器控制,它们控制探针22和音叉16而不是平板12的运动。该方案允许使用共振扫描方法在样品上方扫描探针,而不是在固定探针下方扫描样品。关于图4使用x-y-z转换器18在x轴上扫描共振器16和探针22,同时在图5和6中依靠连接到平板12的转换器70提供扫描期间在扫描方向(x方向)上探针/样品相对运动的控制。这样,当探针固定时可以在两个轴上扫描样品,或者当样品固定时可以在两个轴上扫描探针,或者可以在一个轴上扫描探针或样品的一个或另一个而通过另一个的运动提供另一个轴上的扫描。在图7的情况中,通过连接到共振器16和探针22的转换器70提供探针/样品相对扫描运动的控制,并且因为起始扫描位置的这种精确度并不是在所有情况中都必需的,所以省略细位置控制。这突出使用所述发明结合共振扫描方法可获得的非常快扫描速度的额外优点。图像速度高于机械噪声的普通频率,并且高于通常在过程定位方法中存在的运动不稳定性。因此,免除通常必需的高精度压电转换器是可能的。Figures 4 to 7 show a schematic implementation of an alternative AFM, indicated generally at 10, using further embodiments of probes constructed in accordance with the present invention. In each case, the
在图4,5和7中,探针尖端22a受到将尖端22a推向样品14的力。在图4的例子中,力是吸引的,并且由施加在探针尖端22a和平板12之间的偏置电压产生。因此,探针尖端22a和平板12跨越电源60的端子串联。为了在探针尖端22a和平板12之间建立所需吸引力,除了阻尼涂层22c之外探针还提供有导电涂层50,以便保证探针具有低Q因子。在图6的情况中,样品14和探针尖端22a放置在密封粘性环境80例如液体环境中。在该实施方案中,跨越导电涂层50和在粘性环境外面的放置在样品平板12下方的第二平板90连接电源60。通过将探针浸没于液体中(在生物样品的情况中将是合乎需要的),可以从探针中省略阻尼涂层22c,因为探针暴露于液体环境中导致探针具有接近1的低Q因子。In FIGS. 4 , 5 and 7 ,
为了认识本发明必需的特征,看执行扫描时所涉及的力的图示表示是有用的。这在图8中说明,它显示与图1相同的设置,并且类似地标示相似组件。参考图8,显示了用根据本发明的原子力显微镜(AFM)的探针扫描的样品1。探针包括从中伸出支撑梁3的基片2,支撑梁3具有安装在远离基片2那端的尖锐探测尖端4。在扫描做准备时,经由探针到AFM的安装在探针基片端2施加向下力(Fexternal)到探针上,移动探针尖端4与样品1接触。为了在扫描期间保持接触,力Fexternal大于仅仅使尖端4开始与样品1接触所需的力。结果当扫描样品时由于Fdirect存在,支撑梁3从其静止位置5向上弯曲。如同前面一样,作为支撑梁弯曲的结果产生与kx成正比的力,并将探针尖端4向下引导向样品表面。In order to appreciate the essential features of the invention, it is useful to look at a graphical representation of the forces involved in performing a scan. This is illustrated in Figure 8, which shows the same setup as Figure 1, and similar components are similarly labeled. Referring to FIG. 8 , there is shown a sample 1 scanned with the probe of an atomic force microscope (AFM) according to the present invention. The probe comprises a
如果根据本发明设计的探针偏离样品表面例如由于遇到凸起部分,两个因素有助于将它回复成接触。这允许即使在高扫描速度下也能获得表面的较好跟踪。首先,如在图3-7所示的实施方案中最清楚地看到,可以调节用来使探针加速接近样品的第二力Fdirect,以便将使探针回到与表面接触所花的时间减小到最小值。基本上与形貌无关的这个力用来减小探针的响应时间。其次,探针涂敷有能量吸收材料(或浸没于液体中),这减小储存在探针中的机械能,并且因此减小前述冲击对其运动的影响,保证它快速获得与表面接触的稳定状态。将探针保持于表面的总回复力现在依赖于:If a probe designed according to the invention deviates from the sample surface, for example by encountering a raised portion, two factors contribute to bringing it back into contact. This allows better tracking of the surface to be obtained even at high scan speeds. First, as seen most clearly in the embodiments shown in FIGS. 3-7 , the second force F direct used to accelerate the probe closer to the sample can be adjusted so as to reduce the amount of time it takes the probe to return to contact with the surface. time is reduced to a minimum. This force, essentially independent of the topography, serves to reduce the response time of the probe. Second, the probe is coated with an energy absorbing material (or submerged in a liquid), which reduces the mechanical energy stored in the probe, and thus reduces the impact of the aforementioned shocks on its motion, ensuring that it quickly acquires a stable contact with the surface state. The total restoring force holding the probe to the surface now depends on:
Fdirect+kxF direct +kx
理想地,附加力Fdirect大于悬臂弯曲力kx。此外,其幅度应当足够大,以便如果探针失去接触使它在大约一个像素内与表面接触。Ideally, the additional force F direct is greater than the cantilever bending force kx. Also, its amplitude should be large enough so that if the probe loses contact it makes contact with the surface within about one pixel.
在图3所示的实施方案中,附加力Fdirect是通过将磁场施加到包含磁性元件例如圆珠或磁性涂层的探针尖端提供的磁力。因此很显然地,磁体在AFM中的定位并不苛刻,只是必须布置成有一个将探针尖端4拖向样品1的向下分力。在随后实施方案中,附加力Fdirect是静电力。In the embodiment shown in Figure 3, the additional force F direct is a magnetic force provided by applying a magnetic field to the probe tip comprising a magnetic element such as a bead or a magnetic coating. It is therefore clear that the positioning of the magnet in the AFM is not critical, it just has to be arranged so that there is a downward component of force that pulls the
在图2所示的实施方案中,附加力Fdirect仍然有利于探针的跟踪性能,但是其原点更精细。当使探针和样品紧密接近时,一般地认为形成连接两者的毛细管颈。人们认为该毛细管颈由在空气中成像时不可避免地在样品环境中存在的在探针-样品接触周围液化的流体产生。在正常操作中,发现了由毛细管颈产生的引导力Fdirect足够大,它在低Q探针上快速形成支配回复力,即Fdirect>kx。这对于亲水表面尤其正确。通过选择具有亲水表面的探针例如氮化硅,保证在探针和样品之间形成毛细管颈是可能的。In the embodiment shown in Fig. 2, the additional force F direct still benefits the tracking performance of the probe, but its origin is finer. When the probe and sample are brought into close proximity, it is generally believed that a capillary neck is formed connecting the two. This capillary neck is thought to result from fluid liquefied around the probe-sample contact that is unavoidably present in the sample environment when imaging in air. In normal operation, it was found that the guiding force F direct generated by the capillary neck is sufficiently large that it quickly forms a dominant restoring force on the low-Q probe, ie F direct > kx. This is especially true for hydrophilic surfaces. By choosing a probe with a hydrophilic surface, such as silicon nitride, it is possible to ensure the formation of a capillary neck between the probe and the sample.
不管附加引导力Fdirect的原点如何,探针的低Q允许当支撑梁伸直时快速地消散所储存的能量,并且通过引导力Fdirect的作用回复探针与样品表面的接触。因此,通过一种机械反馈回路实现探针对样品表面的跟踪,它比依赖于悬臂弯曲力kx的现有技术跟踪机制动作更快。Regardless of the origin of the additional guiding force F direct , the low Q of the probe allows the stored energy to be quickly dissipated when the support beam straightens and the contact of the probe to the sample surface is restored by the action of the guiding force F direct . Thus, the tracking of the probe to the sample surface is achieved through a mechanical feedback loop that is faster than prior art tracking mechanisms that rely on the cantilever bending force kx.
在这里所描述的显微镜中,探针端在显著高于其第一振荡模式的频率下作出响应。因此,在探针弯曲和其垂直位置之间不再有简单关系,因为现在弯曲程度将依赖于它已在那个垂直位置多长时间。因此,使用基于从探针背面到分立光电二极管的激光反射的方法而获得的图像将不对应于表面的形貌,而是对应于形貌和梯度的组合。为了获得确实对应于形貌的图像,可以例如使用干涉仪测量方法监测探针的位移。例如,光纤干涉仪可用来监测探针端相对于光纤的位置,或者基于Wollaston棱镜的干涉仪可用来监测探针端相对于另一点的位置,或者干涉显微镜可用来监测探针端的位置,在该情况中显微镜视场中的与探针端对应的位置处的光强度将依赖于其垂直位置而改变。无论使用哪个方法,现在可以获得对应于表面形貌的图像,对于度量衡特别适用。In the microscope described here, the probe tip responds at a frequency significantly higher than its first oscillation mode. Thus, there is no longer a simple relationship between the bending of the probe and its vertical position, since now the degree of bending will depend on how long it has been in that vertical position. Thus, images obtained using methods based on reflection of laser light from the back of the probe to discrete photodiodes will not correspond to the topography of the surface, but to a combination of topography and gradients. In order to obtain an image that does correspond to the topography, the displacement of the probe can be monitored, for example using interferometric measurements. For example, a fiber optic interferometer can be used to monitor the position of the probe end relative to the fiber, or a Wollaston prism-based interferometer can be used to monitor the position of the probe end relative to another point, or an interference microscope can be used to monitor the position of the probe end, where In this case the light intensity at the position in the field of view of the microscope corresponding to the tip of the probe will vary depending on its vertical position. Whichever method is used, it is now possible to obtain images corresponding to surface topography, especially for metrology.
为了有助于实现Fdirect>kx,应当进一步将探针设计成具有相对低的弹簧常数。典型地,这应当小于1Nm-1,可以通过使用适当成形的探针来实现这点。在本发明中,悬臂偏转仅对定义探针所处空间中的位置,即探针和样品之间的相互作用力有用,使得允许收集图像。To help achieve F direct >kx, the probe should further be designed with a relatively low spring constant. Typically this should be less than 1 Nm -1 , which can be achieved by using an appropriately shaped probe. In the present invention, the cantilever deflection is only useful to define the position in space where the probe is located, ie the interaction forces between the probe and the sample, allowing images to be collected.
在一种原型探针设计中,悬臂具有0.01至0.06Nm-1的典型弹簧常数。可接受范围依赖于待成像特征的高度。对于50nm高的特征,原型探针将施加0.5nN至3nN的回复力。施加到尖端的引导力估计为1-100nN的量级,由源自毛细管颈的力和例如由图4,5和7中所示设置产生的静电力的组合产生。可以控制静电力的大小以便使图像最优化。设置这点,所以对于最快所需响应从而最大尖端速度,可能的最高力提供到尖端,它不会在研究中损伤或破坏表面。In one prototype probe design, the cantilever has a typical spring constant of 0.01 to 0.06 Nm −1 . The acceptable range depends on the height of the features to be imaged. For features 50nm high, the prototype probe will exert a restoring force of 0.5nN to 3nN. The guiding force applied to the tip is estimated to be on the order of 1–100 nN, resulting from a combination of forces originating from the capillary neck and electrostatic forces such as those generated by the setup shown in Figs. 4, 5 and 7. The magnitude of the electrostatic force can be controlled to optimize the image. This is set so that for the fastest desired response and thus maximum tip velocity, the highest force possible is supplied to the tip, which does not damage or break the surface under study.
与依靠悬臂力形成对照在样品跟踪时利用引导回复力Fdirect的能力代表优于现有技术的显著改进。通过提供具有储存机械能的降低能力的探针,作用于探针上的主要力是引导力Fdirect,以及由于探针对表面的即时弯曲产生的力,并且引导力Fdirect是支配力。不管引导力是依靠毛细管颈产生的“自然”力,还是附加的外力例如经由磁珠施加的力,这都适用。在任一种情况中,回复力具有基本上与探针位置无关的幅度。作为对比,现有技术回复力kx的幅度依赖于悬臂离其静止位置的位移x。因此在样品特别高的位置产生高回复力。如果允许回复力以该方式改变,那么始终保证样品不被损伤是非常困难的。根据本发明而实施的回复机制具有与样品高度大大无关的幅度。The ability to utilize the guided restoring force F direct in sample tracking as opposed to relying on cantilever forces represents a significant improvement over the prior art. By providing a probe with a reduced ability to store mechanical energy, the main force acting on the probe is the directing force F direct , and the force due to the immediate bending of the probe against the surface, and the directing force F direct is the dominant force. This applies regardless of whether the guiding force is by means of a "natural" force generated by the capillary neck, or an additional external force such as that applied via a magnetic bead. In either case, the restoring force has a magnitude that is substantially independent of probe position. In contrast, the magnitude of the prior art restoring force kx depends on the displacement x of the cantilever from its rest position. High restoring forces are thus generated at particularly high positions on the sample. If the restoring force is allowed to vary in this way, it is very difficult to consistently ensure that the sample is not damaged. The recovery mechanism implemented in accordance with the present invention has a magnitude that is largely independent of sample height.
如所说明的,外加力是磁力不是基本的,虽然优选地它是幅度不依赖于样品高度的力。有朝向表面的净力使得来自探针中存在的振荡模式的任何力不会导致探针离开表面是必需的。因此,引导力Fdirect越大,对通过涂层的能量吸收和消散的预期要求越不严厉。在这一点上,虽然用仅依靠毛细管颈作为Fdirect源的低Q悬臂实现本发明是可能的,优选地也施加与偏转无关的外力。如这里所描述的实施方案中所说明的,受到静电力或磁力的探针是更可控制的,并且提供用于形成最高品质图像的更多选项。As stated, it is not essential that the applied force is magnetic, although preferably it is a force whose magnitude does not depend on the height of the sample. It is necessary that there is a net force towards the surface such that any force from the oscillatory modes present in the probe does not cause the probe to leave the surface. Therefore, the larger the directing force F direct , the less stringent the expected requirements on energy absorption and dissipation through the coating. In this regard, while it is possible to implement the invention with a low-Q cantilever relying only on the capillary neck as a source of F direct , it is preferable to also apply an external force independent of deflection. As illustrated in the embodiments described herein, probes subjected to electrostatic or magnetic forces are more controllable and provide more options for forming the highest quality images.
图9a-9f清楚地说明本发明探针优于常规AFM装置的性能提高。图9a,9b和9c都是相同表面区域的图像,并且类似地图9d,9e和9f都是另一表面区域的图像。在所有情况中,标尺表示1微米,并且表面被成像的材料是安装在玻璃基体上的结晶聚环氧乙烷(PEO)。图9a和9d是使用本发明探针生成的图像,而图9b和9e是使用常规AFM监测探针高度的改变而生成的图像,并且图9c和9f是使用常规AFM监测偏转改变而生成的图像。为了生成图9a和9d的图像,连同涂敷有薄聚合物膜的商业上可获得的悬臂一起使用具有NanoscopeTM IV控制器的Veeco Dimension 3100TM AFM。样品安装在由石英晶体共振器和5微米压电堆(P-802和E-505,PhysikInstrument,Germany)构成的微共振扫描器上。为了收集图9a和9d的数据,使用Infinitesima有限公司的共振扫描控制器。Figures 9a-9f clearly illustrate the improved performance of the probes of the present invention over conventional AFM devices. Figures 9a, 9b and 9c are all images of the same surface area, and similar maps 9d, 9e and 9f are images of another surface area. In all cases, the scale bar represents 1 micron and the material on which the surface was imaged was crystalline polyethylene oxide (PEO) mounted on a glass substrate. Figures 9a and 9d are images generated using the probe of the present invention, while Figures 9b and 9e are images generated using conventional AFM monitoring changes in probe height, and Figures 9c and 9f are images generated using conventional AFM monitoring deflection changes . To generate the images of Figures 9a and 9d, a Veeco Dimension 3100 ™ AFM with a Nanoscope ™ IV controller was used together with a commercially available cantilever coated with a thin polymer film. Samples were mounted on a microresonant scanner consisting of a quartz crystal resonator and a 5 micron piezoelectric stack (P-802 and E-505, PhysikInstrument, Germany). To collect the data for Figures 9a and 9d, a resonant scan controller from Infinitesima Ltd. was used.
图9a和9d在仅14.3ms时段上由128×128像素阵列构成,在每个图像的中心附近探针尖端速度分别是22.4cms-1和16.8cms-1。Figures 9a and 9d consist of 128x128 pixel arrays over a period of only 14.3 ms, with probe tip velocities of 22.4 cms -1 and 16.8 cms -1 near the center of each image, respectively.
因此通过本发明,和图像收集可能花费30秒以上的常规AFM不同,可以在毫秒内生成几微米区域的图像。虽然可以用与常规AFM显微镜当前所使用速度相同的扫描尖端速度来操作所示的实施方案,实施方案允许0.1cms-1以上的尖端速度,并且依赖于样品表面的平整度可以获得超过50.0cms-1的尖端速度。例如,用22.4cms-1的尖端速度可以在14.3ms内成像4.4×4.4微米的区域,并且在8.3ms内成像1.5×1.5微米的区域。此外,即使以该速度,用软聚合物表面可获得具有好于10nm横向和1nm竖向分辨率的图像。Thus with the present invention, images of regions of a few microns can be generated within milliseconds, unlike conventional AFMs where image collection can take upwards of 30 seconds. While the illustrated embodiment can be operated with scanning tip velocities identical to those currently used by conventional AFM microscopes, the embodiment allows for tip velocities above 0.1 cms , and depending on the flatness of the sample surface, over 50.0 cms can be obtained . 1 tip speed. For example, a 4.4 x 4.4 micron area can be imaged in 14.3 ms and a 1.5 x 1.5 micron area can be imaged in 8.3 ms with a tip speed of 22.4 cms −1 . Furthermore, even at this speed, images with better than 10 nm lateral and 1 nm vertical resolution can be obtained with soft polymer surfaces.
已经进一步观察到,在这些探针尖端速度下,与在较低速度下相比样品似乎更不易受损伤。当探针尖端在每个点处花费较少时间时,样品受到较小变形,因此较小可能达到它开始塑性变形的那一点。使用本发明,样品的表面可以受到大约为108ms-1的剪切速率,这是许多聚合物例如表现出玻璃特性的速率。一般地,已经发现了更高频率可能使粘弹性液体降低到玻璃转变温度以下,因此改变探针看起来导致对样片较小损伤的表面性质。It has further been observed that at these probe tip velocities the sample appears to be less susceptible to damage than at lower velocities. When the probe tip spends less time at each point, the sample is subject to less deformation and is therefore less likely to reach the point where it begins to deform plastically. Using the present invention, the surface of a sample can be subjected to a shear rate of about 10 8 ms -1 , which is the rate at which many polymers, for example, exhibit glass properties. In general, it has been found that higher frequencies are likely to lower the viscoelastic fluid below the glass transition temperature, thus changing the surface properties of the probe that appear to cause less damage to the coupon.
本发明的探针选择成具有低Q,理想地使得任何引发的振荡被强烈地阻尼。如同这里所描述的,最优选实施方案以及依靠由毛细管颈产生的自然回复力足够有效地允许改进跟踪的方案,在于用能量吸收材料如聚合物膜涂敷探针的支撑梁的一侧或两侧。特别地如果施加大的磁力(或其他附加力),保证低Q的可选方法是通过探针形状的明智选择。另一种可选方案简单地通过在扫描期间将探针浸没到粘性/液体环境中来提供低Q因子。又一种可选方案是例如在支撑梁由能够满足提供较低有效Q因子的电响应材料形成或包括这种电响应材料的情况中,用电学方法改变探针的支撑梁的性质。The probes of the present invention are chosen to have a low Q, ideally so that any induced oscillations are strongly damped. As described here, the most preferred embodiment, and one that relies on the natural restoring forces generated by the capillary necks to be sufficiently effective to allow improved tracking, consists in coating one or both sides of the probe's support beam with an energy absorbing material such as a polymer film. side. An alternative way to ensure low Q is through judicious choice of probe shape, especially if large magnetic forces (or other additional forces) are applied. Another alternative provides a low Q-factor simply by submerging the probe into a viscous/liquid environment during scanning. Yet another option is to electrically alter the properties of the support beam of the probe, for example where the support beam is formed of or includes an electrically responsive material capable of providing a lower effective Q factor.
支撑梁、探针尖端和任何附加组件如磁珠理想地具有低质量。对于给定的回复力,这自然地增加尖端返回表面的加速度,因此更好地允许探针跟踪表面。Support beams, probe tips, and any additional components such as magnetic beads are ideally of low mass. For a given restoring force, this naturally increases the acceleration of the tip returning to the surface, thus better allowing the probe to track the surface.
支撑梁可以具有预定设计,使得促进理想响应。也就是,使作为当探针跟踪样品时弯曲的结果产生的方向相关回复力达到最小,以及如果探针离开表面时阻尼振荡响应(低Q因子)。虽然在这里经常称为悬臂设计,这仅仅是因为利用修改的现有技术AFM到该新目的。现有技术AFM利用悬臂探针。本发明所必需的是探针尖端必须具有相对于样品可定义的横向位置(x,y平面)以及在z方向上的自由运动。现有技术AFM悬臂探针可以容易地执行该功能,但它不代表唯一的解决方案。The support beams may have a predetermined design such that a desired response is promoted. That is, minimizing direction-dependent restoring forces that arise as a result of bending when the probe tracks the sample, and damping the oscillatory response (low Q-factor) if the probe is off the surface. Although often referred to here as a cantilever design, this is simply because of the use of a modified prior art AFM to this new purpose. Prior art AFM utilizes cantilever probes. Essential to the invention is that the probe tip must have a definable lateral position (x,y plane) relative to the sample and free movement in the z direction. A prior art AFM cantilever probe can easily perform this function, but it does not represent the only solution.
回到包括探针尖端的支撑梁的实施方案,图10说明从上文看来更精密复杂的各种可能设计特征,其有利于减小回复力并降低Q因子。可以结合每个设计使用这里所描述的聚合物涂层,以进一步调节响应。图10(c)显示更常规的梁形状,而图10(a)和(b)描绘可选的可能性。在每个设计中,区域1至4被突出化,每个区域设计成具有特定性质。每个图(a)至(c)说明从基片向前延伸的一个或多个支撑梁。Returning to the embodiment of the support beam including the probe tip, Fig. 10 illustrates various possible design features that appear to be more sophisticated from the above, which facilitate reducing restoring forces and lowering the Q-factor. The polymer coatings described here can be used in conjunction with each design to further tune the response. Figure 10(c) shows a more conventional beam shape, while Figures 10(a) and (b) depict alternative possibilities. In each design, regions 1 to 4 are highlighted, and each region is designed to have specific properties. Each of figures (a) to (c) illustrates one or more support beams extending forwardly from the substrate.
区域1在所有情况中都是枢轴点。也就是,在该区域附近悬臂梁以弧形摆动。因此区域1具有沿着z轴的非常低的弹簧常数(理想地<0.01Nm-1),以及在x,y平面内的非常高的弹簧常数。这样,相对于基片位置规定了尖端的横向位置,但对于小偏转也允许垂直于样品表面自由地移动。Area 1 is the pivot point in all cases. That is, the cantilever beam swings in an arc around this region. Region 1 thus has a very low spring constant (ideally <0.01 Nm −1 ) along the z-axis, and a very high spring constant in the x,y plane. In this way, the lateral position of the tip is specified relative to the substrate position, but also allows free movement perpendicular to the sample surface for small deflections.
区域2形成基本梁结构。它应当是硬的并具有高的基本共振频率。
区域3是连接梁和尖端区域的弯曲区域,它允许尖端向上和向下移动。选择该区域的弹簧常数,使得尖端的共振频率高于探针的响应时间,即大于机械反馈回路的带宽。该区域也应当是涂敷聚合物的,以便在空气中提供阻尼。但是如果在液体中成像,由于液体环境的能量消散性质,大大地克服了对涂层的需要。
区域4是尖端区域。探针尖端粘附着其下表面,或者形成其下表面的一部分。区域面积必须足够大,使得通过位置检测系统确定其位置,对于光杠杆和其他远场光学系统,基本上是横向尺寸大于几个微米。
在施加外部引导力到探针上以便将它推向表面的实施方案中,响应于该力的元件可以放置到尖端区域4、梁区域2或两者上。但优选地,它放置在尖端上。In embodiments where an externally directed force is applied to the probe to push it toward the surface, elements responsive to this force may be placed on the
图11和12说明形成梁中的低和受控弹簧常数的例子。基本上如图11所示,这涉及在支撑梁的所需位置处形成孔洞。与图11(a)相比,图11(b)和(c)中所示的设计提供增加的横向稳定性。孔洞形状可以改变,例如像图12中所示的,以便控制聚合物涂层的性质。也就是,曲线的、方形的或其他形状孔洞不同地影响聚合物涂层在梁表面上形成的方式,这又影响悬臂的阻尼性质。Figures 11 and 12 illustrate examples of low and controlled spring constants in forming beams. Essentially as shown in Figure 11, this involves forming holes in the support beams at desired locations. The design shown in Figures 11(b) and (c) provides increased lateral stability compared to Figure 11(a). The hole shape can be varied, for example as shown in Figure 12, in order to control the properties of the polymer coating. That is, curved, square, or other shaped holes differently affect the way the polymer coating forms on the beam surface, which in turn affects the damping properties of the cantilever.
提供探针支撑梁的预定设计的优点在于,它允许分开对振荡阻尼和减小偏转相关回复力的不同要求。特别地,可以这样设计,使得当遇到样品表面的高区域时仅激发主模式。因此,与现有技术悬臂梁的多模式要求形成对比,仅需要例如通过其涂层保证梁具有关于该模式的低Q因子。An advantage of providing a predetermined design of the probe support beam is that it allows separating the different requirements for oscillation damping and reducing deflection related restoring forces. In particular, it can be designed such that only the main mode is excited when high regions of the sample surface are encountered. Thus, in contrast to the multimode requirement of prior art cantilever beams, it is only necessary to ensure that the beam has a low Q-factor with respect to the mode, for example by its coating.
应当注意图2至7中所示的装置只是示例AFM的说明。有许多种可以实施本发明的不同AFM实施方案,所有这些方案省略了作为获得图像的基本方法的探针高度的常规反馈控制。例如,安装在共振器例如音叉上不是必需的。该方案只是在这些实施方案中使用以便说明本发明在利用共振振荡的快速扫描技术上适用性。它同样可适用于较慢的扫描方法中。探针22可选地可以代替样品14振荡。使用该可选实施方案,可以想像在利用光学技术监测探针位移的情况中,成像梁足够宽以包括快速扫描轴。It should be noted that the arrangements shown in Figures 2 to 7 are illustrations of example AFMs only. There are many different AFM implementations in which the invention can be practiced, all of which omit the conventional feedback control of probe height as a fundamental method of acquiring images. For example, mounting on a resonator such as a tuning fork is not necessary. This scheme is used in these embodiments only to illustrate the applicability of the invention to fast scanning techniques using resonant oscillations. It also applies to slower scanning methods. Probe 22 can optionally be oscillated instead of
可以通过不同于光杠杆技术的方法测量探针偏转/位移。本领域中已知的可选技术包括干涉仪测量法和压电式涂敷探针,以及对受热探针的辐射输出的热变化的探测。由于探针作出响应的频率,探针偏转数据同时代表着样品表面的形貌和空间特征的频率,通过利用干涉仪测量法监测探针的偏转/位移,从探针偏转数据中单纯地提取样品表面的形貌数据是可能的。并且,虽然使用压电传动器来样品平板/探针的运动是优选的,也可以设想其他传动器包括例如控制杆的热膨胀。Probe deflection/displacement can be measured by methods other than optical lever technology. Alternative techniques known in the art include interferometric measurements and piezoelectrically coated probes, as well as detection of thermal changes in the radiant output of heated probes. Due to the frequency at which the probe responds, the frequency at which the probe deflection data represents both topography and spatial features of the sample surface, is simply extracted from the probe deflection data by monitoring the deflection/displacement of the probe using interferometric measurements Surface topography data is possible. Also, while the use of piezoelectric actuators for sample plate/probe movement is preferred, other actuators including, for example, thermal expansion of levers are contemplated.
虽然已根据提供能量吸收涂层到探针的支撑梁描述探针的Q因子的控制,可以设想用于控制探针的Q因子的其他装置,包括电控制。Although the control of the probe's Q-factor has been described in terms of providing an energy-absorbing coating to the probe's support beam, other means for controlling the probe's Q-factor can be envisioned, including electrical control.
为了成像比探针的扫描区域更大的表面区域,可以生成不同的通常相邻的区域的分立连续图像,然后组合以构成该大区域上的图像。步进电机或其他传动器可以用来在对每个独立图像的细位置调节之前在分立图像之间移动探针和/或样品平板。理想地选择各个扫描区域并交迭,使得各个图像的对准的可视确认是可能的。In order to image a surface area larger than the probe's scanning area, separate, sequential images of different, often adjacent, areas can be generated and then combined to form an image over this large area. Stepper motors or other actuators can be used to move the probe and/or sample plate between discrete images prior to fine positional adjustments for each individual image. The individual scan areas are ideally selected and overlapped such that visual confirmation of the alignment of the individual images is possible.
如果使用音叉16,那么它可以是商业上可获得的多种音叉的一种,或者具有预定设计以便提供期望的振荡频率。合适的例子是具有32kHz共振频率的石英晶体音叉。当它设计成具有高的各向异性机械性质时,音叉很好地适合于本应用。因此,它的共振是独立的,并且可以单独地激发,所以仅局限于样品平面内的那个(或那些)。重要的是,可以在一个方向上使音叉16共振,并在另一个方向上扫描,而不在模式之间发生耦合。因此当样品14被探针22探究时,允许样品14的稳定快速运动。可以使用具有良好分离的横向和竖向共振的类似便利的可选机械共振器来代替音叉。If a
本发明不局限于单纯AFM操作,虽然需要在探针和样品表面之间有力相互作用。但是该操作模式也可以与设计来监测探针和样品之间的其他相互作用或相互作用指示的显微镜组件结合。其他相互作用的例子可以包括光学、电容性、磁性、剪切力,或热相互作用。其他指示包括振荡幅度、轻敲或剪切力、电容或感生电流。例如在UK专利申请0310344.7号中描述了一般探针显微镜的这些不同的操作模式。The present invention is not limited to pure AFM operation, although a vigorous interaction between the probe and the sample surface is required. But this mode of operation can also be combined with microscope components designed to monitor other interactions or indications of interactions between the probe and the sample. Examples of other interactions may include optical, capacitive, magnetic, shear, or thermal interactions. Other indications include oscillation amplitude, tapping or shear force, capacitance or induced current. These different modes of operation of a general probe microscope are described, for example, in UK Patent Application No. 0310344.7.
AFM中所利用的探针与样品表面的相互作用也使影响表面的性质从而故意地“写”信息到样品上变得可能。该技术称为纳米光刻术,并且AFM广泛地用于该目的。例如,通过施加电压到导电悬臂上可以氧化样品圆片的金属层的区域。利用双光子吸收和光刻胶的聚合的另一个例子在Appl.Phys,Lett. 81(193663(2002)中的Xiaobo Yin等人的“使用无孔光学探针的近场双光子纳米光刻术”中描述。在这两个例子中,非常小的探针尺寸允许以非常高的密度写入信息。本发明的AFM和悬臂探针也可以适用于在纳米光刻术中使用。通过本发明改进表面跟踪的能力不仅提供比先前获得的更快写时间的可能性,而且提供增加图像分辨率即写密度的可能性。为了使它更适合于在纳米光刻中使用,探针尖端可以是导电的,它可以是涂敷金属的,以便增加它与表面的光学相互作用,或者它可以涂敷有选定分子物质以便在沾笔蚀刻印刷应用中使用。The interaction of probes with the sample surface utilized in AFM also makes it possible to deliberately "write" information onto the sample by influencing the properties of the surface. This technique is called nanolithography, and AFM is widely used for this purpose. For example, regions of the metal layer of the sample wafer can be oxidized by applying a voltage to the conductive cantilever. Another example using two-photon absorption and polymerization of photoresists is in Xiaobo Yin et al., "Near-field two-photon nanolithography using non-porous optical probes" in Appl. Phys, Lett. 81 (193663 (2002) described in ". In both examples, the very small probe size allows information to be written at very high densities. The AFM and cantilever probes of the present invention can also be adapted for use in nanolithography. Through the present invention The ability to improve surface tracking offers the possibility not only of faster write times than previously obtained, but also of increased image resolution, i.e. write density. To make it more suitable for use in nanolithography, the probe tip can be Conductive, it can be metallized to increase its optical interaction with the surface, or it can be coated with selected molecular species for use in dip pen etch printing applications.
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| Application Number | Priority Date | Filing Date | Title |
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| GB0316577A GB0316577D0 (en) | 2003-07-15 | 2003-07-15 | Atomic force microscope |
| GB0316577.6 | 2003-07-15 | ||
| GB0323229.5 | 2003-10-03 | ||
| GB0408234.3 | 2004-04-13 |
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| CN1836290A true CN1836290A (en) | 2006-09-20 |
| CN100592088C CN100592088C (en) | 2010-02-24 |
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| CN102483429A (en) * | 2009-08-07 | 2012-05-30 | 施佩克斯表面纳米分析股份有限公司 | Metal tip for scanning probe device and method of manufacturing same |
| CN102495043A (en) * | 2011-12-14 | 2012-06-13 | 中国科学院苏州纳米技术与纳米仿生研究所 | Device and method for measuring surface defect of semiconductor material |
| CN103869103A (en) * | 2014-03-27 | 2014-06-18 | 上海华力微电子有限公司 | AFM probe device |
| CN105807792A (en) * | 2016-03-09 | 2016-07-27 | 西安交通大学 | On-chip controller of scanning ion conductance microscope and control method |
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| DE4435635A1 (en) * | 1994-10-06 | 1996-06-05 | Inst Physikalische Hochtech Ev | Microfabrication of cantilever stylus for atomic force microscopy |
| JP3210961B2 (en) * | 1997-04-15 | 2001-09-25 | 北海道大学長 | Measuring device for exchange interaction force |
| US6245204B1 (en) * | 1999-03-23 | 2001-06-12 | Molecular Imaging Corporation | Vibrating tip conducting probe microscope |
| US6349591B1 (en) * | 2000-01-13 | 2002-02-26 | Universite Pierre & Marie Curie | Device and method for controlling the interaction of a tip and a sample, notably for atomic force microscopy and nano-indentation |
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2003
- 2003-07-15 GB GB0316577A patent/GB0316577D0/en not_active Ceased
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- 2004-07-15 CN CN 200480023496 patent/CN100592088C/en not_active Expired - Fee Related
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| Publication number | Publication date |
|---|---|
| GB0316577D0 (en) | 2003-08-20 |
| CN100592088C (en) | 2010-02-24 |
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