X-ray diffraction

X-ray diffraction is the angular redistribution of X-ray wave intensity through wave interference between scattered waves. In a crystal structure, repeated lattice translations select discrete outgoing directions by the Laue equations. A photographic plate can therefore turn invisible atomic periodicity into a visible constellation of spots. Their geometry constrains the Bravais lattice and its orientation; their wave intensities also depend on the crystal basis structure factor. Determining atomic positions belongs to X-ray crystallography and requires more information than recognizing a spot pattern.

The Laue X-ray diffraction experiment of 1912 established this phenomenon experimentally. The Laue method uses a fixed crystal structure with a range of incident wavelengths; the Bragg crystal reflection experiment of 1913 instead measured angularly resolved signals with a moving detector. These are different ways of finding the same coherent elastic scattering directions.

A powder-diffraction camera with photographic film wrapped around a cylindrical specimen axis. Diffraction cones intersect the film in paired curved lines; angular position along the cylindrical film differs from the $R=L\tan 2\theta$ relation for a forward flat plate. Back reflections can also be recorded.

Diffraction from an oriented single crystal. A reflection requires both an allowed nonzero structure factor and access to its reciprocal-lattice direction and Bragg angle.

A geometry in which the diffracted beam traverses the specimen and exits another surface. Absorption and thickness affect whether it is observable.

Reflection diffraction from planes inclined to the specimen surface. Incident and exit angles relative to the surface differ; both must correspond to rays on the accessible side of an opaque specimen.

A diffraction geometry in which the incident and diffracted rays make equal angles with the specimen surface. The selected reciprocal-lattice vector is normal to that surface.

An X-ray diffractometer measures scattering intensity as a function of sample orientation, scattering angle or photon energy. Its essential elements are an incident X-ray beam, a mounted sample, controlled angular geometry and a detector recording the outgoing beam or pattern.

A monochromatic angle scan changes which reciprocal-lattice vectors satisfy the elastic diffraction condition. A position-sensitive detector can instead record many outgoing directions at once, while sample rotation brings further reflections into view. Converting the counts into structural information requires the wavelength, angular calibration, sample alignment and intensity corrections. A single crystal and a powder produce different sampling patterns. The recorded intensities contain both peak-position information about the lattice and structure-factor information about the atomic basis.

Powder X-ray diffraction measures X-ray diffraction from many crystal grains with different orientations. For each allowed set of lattice spacings, suitable grains satisfy Bragg's law and produce a cone of diffracted directions, seen as a ring on an area detector or a peak in an angular scan. Several peak positions and systematic absences can identify a crystal structure even when a sample no longer retains one single-crystal orientation. Preferred orientation, strain and phase coexistence can complicate interpretation.

At fixed radiation wavelength, differentiating Bragg's law for an isotropically expanding cubic specimen gives the displayed angular sensitivity, with angles in radians. Accurate temperature inference requires a calibrated lattice-parameter versus temperature curve, stable wavelength and angular zero, and separation of thermal expansion from stress or composition shifts. Counting statistics can permit centroid precision finer than the observed diffraction-line width.

For cubic diffraction, $4{\sin }^2\theta /{\lambda }^2=(h^2+k^2+l^2)/a^2$. Ratios identify the allowed integer sequence after applying both FCC centring and diamond-basis selection rules. A common sequence starts $3,8,11,16,19$ for111,220,311,400,331. The absolute parameter remains proportional to the explicitly selected radiation wavelength.

For incident and outgoing unit propagation vectors ${\mathbf{s}}_{\mathrm{in}}$ and ${\mathbf{s}}_{\mathrm{out}}$, wavelength $\lambda >0$, and primitive lattice translation vectors $a_1,a_2,a_3$, the Laue equations areAll three must hold for the same wavelength and outgoing direction. The integers label a reciprocal lattice vector; they need not be coprime. For wavevectors ${\mathbf{k}}_{\mathrm{in},\mathrm{out}}=(2\pi /\lambda ){\mathbf{s}}_{\mathrm{in},\mathrm{out}}$, equivalentlyThis uses angular wavenumbers; the crystallographic convention without $2\pi$ instead uses $\mathbf{s}/\lambda$.^[ref]

For a short proof, translate a scatterer through $a_i$. Its incident wave phase changes by ${\mathbf{k}}_{\mathrm{in}}\cdot a_i$ and propagation to the same distant observation direction contributes $-{\mathbf{k}}_{\mathrm{out}}\cdot a_i$. The relative wave phase factor is therefore $\exp (-i\mathbf{G}\cdot a_i)$. It equals one for all lattice translations exactly when $\mathbf{G}$ belongs to the reciprocal lattice. A finite crystal lattice structure factor broadens the ideal maxima; the crystal basis structure factor can cancel them. Geometric phase matching is necessary for a sharp reflection, but does not guarantee a visible spot.

For elastic scattering, the additional constraint isIt is an Ewald sphere centered at $-{\mathbf{k}}_{\mathrm{in}}$ in the space of transfer vectors $\mathbf{G}$. The parent elastic Bragg scattering condition uses $q={\mathbf{k}}_{\mathrm{in}}-{\mathbf{k}}_{\mathrm{out}}=-\mathbf{G}$, so its displayed condition has the opposite sign. Both give Bragg's law for the same lattice planes.

In the Laue method, a fixed single crystal structure receives a collimated beam containing many wavelengths. Each reciprocal lattice vector can select its own wavelength; waves with different wavelengths need not interfere with one another. For $\mathbf{G}\ne 0$, the elastic scattering constraint gives the particularly useful testA candidate reflection requires ${\lambda }_{\mathbf{G}}>0$ within the source spectrum and an outgoing ray that reaches the detector. Varying wavelength changes the radius and center of the Ewald sphere while leaving the reciprocal lattice fixed. A monochromatic wave instead fixes the radius: rotating the crystal structure or varying the incident wavelength in a scan finds reflections sequentially. A white-beam photograph integrates many spectral selections in one exposure; it is not an angular scan at one known wavelength.

The Laue method is useful for orienting a single crystal structure: tilting it changes which reciprocal lattice vectors meet the spectral and detector conditions. Absolute scale has an ambiguity if the wavelengths are unknown. Scaling all direct lattice translations by $c>0$ and all selected wavelengths by $c$ leaves every outgoing direction unchanged. Independently known spectral information or length calibration is needed to remove this ambiguity.

Choose a primitive cubic lattice with $a=0.400\mathrm{nm}$, one identical point scatterer per primitive unit cell, incident direction ${\mathbf{s}}_{\mathrm{in}}=(0,0,1)$, and the continuous wavelength band $0.080\le \lambda \le 0.160\mathrm{nm}$. This is a hypothetical model, not the zinc blende specimen of the Laue X-ray diffraction experiment of 1912. Write a candidate reciprocal lattice vector as $\mathbf{G}=(2\pi /a)(h,k,-m)$ with $m>0$, and set $S=h^2+k^2+m^2$. The Laue equations and elastic scattering giveA transmission photographic plate at $z=L>0$ intercepts only $s_{\mathrm{out},z}>0$. Its coordinates relative to the direct beam areFor $(h,k,-m)=(2,1,-1)$ and $L=50\mathrm{mm}$, $S=6$, $\lambda =0.13333\dots \mathrm{nm}$ and ${\mathbf{s}}_{\mathrm{out}}=(2/3,1/3,2/3)$, so $(X,Y)=(50,25)\mathrm{mm}$. Its length is one, and each component difference satisfies the corresponding Laue equations. This verifies a direction and a selected wavelength, without predicting an exposure or measured wave intensity.

The first panel has fourfold symmetry because its chosen Bravais lattice, beam axis and square detector share that symmetry. For the tilted panel, apply a rotation matrix $R$ to each index vector, set $v=R(h,k,l)$, and use $\lambda =-2a{v}_z/|v{|}^2$ and ${\mathbf{s}}_{\mathrm{out}}=(0,0,1)+(\lambda /a)v$. All indices with $|(h,k,l)|\le 2a/{\lambda }_{\min }=10$ suffice: elastic scattering bounds $|\mathbf{G}|\le 2|{\mathbf{k}}_{\mathrm{in}}|$. Thus the plotted spectral and angular selection is complete within this ideal point model and detector window. Multiples of an index vector select inversely scaled wavelengths and can land on the same spot; a white-beam spot need not identify a unique diffraction order.

Max von Laue proposed crystal X-ray diffraction and wrote the theoretical section; Walther Friedrich and Paul Knipping performed the experiments.^[ref]

An X-ray tube, lead apertures and shielding supplied a narrow beam through a crystal on a goniometer. Photographic plates recorded the direct beam and separate spots. Copper(II) sulfate trials preceded oriented zinc blende. Optical alignment was checked with X-rays. Removing the crystal removed the extra spots; grinding destroyed their ordered arrangement; translation preserved it, while tilt changed it. Rotation about the beam rotated the pattern.^[ref]

Spots and orientation dependence supported wave interference and three-dimensional crystal periodicity. They determined neither all atomic positions nor an absolute wavelength scale. The authors left open whether the selected radiation originated as crystal fluorescence or was already in the incident beam. This differs from the modern Laue method.^[ref]

The 1914 Nobel Prize in Physics went to Max von Laue; the discovery's experimental account remains jointly credited to Walther Friedrich and Paul Knipping.^[ref] The subsequent inference of particular crystal structures is developed under X-ray crystallography.